JPH11193266A - Silver halide photographic material and its treatment and formazane compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic material excellent in image quality such as sharpness, graininess, resolving power or color reproducibility and providing a stable and ultrahigh contrast image even by treatment with a developer at a relatively low pH. SOLUTION: This silver halide photographic material contains at least one kind of compound oxidized with an oxidized form of a developing agent and convertible into a development retarder, e.g. a compound represented by the following general formula (R, R' and R" denote each hydrogen atom or a monovalent substituent group) in the silver halide photographic material having at least one layer of a silver halide emulsion layer.

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 containing a compound exhibiting a development inhibiting effect corresponding to an image density in a development processing step. Relates to a silver halide photographic light-sensitive material suitable for use in photoengraving. The present invention also relates to a novel formazan compound used for improving the photographic performance of a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art There has been known a compound which releases a photographically useful group through an oxidation-reduction reaction and exerts a development inhibiting effect corresponding to the image density in a development processing step. Improvements in the photographic characteristics of silver halide photographic light-sensitive materials have been made.

[0003] In silver halide photographic light-sensitive materials used for photoengraving, with the diversification and complexity of printed matter, the Ming Dynasty.
There is a strong demand for improved reproducibility of original documents in Gothic characters, copy dots, and eye-opening work.

The photoengraving step includes a step of converting a continuous tone original into a halftone image. In the process of converting the image into a halftone dot image, a technique capable of reproducing a super-high contrast image is desired. In order to reproduce a super-high contrast image, conventionally, for example, Japanese Patent Application Laid-Open No. 56-106244, etc. Hydrazine derivatives as described have been used. According to the method using this hydrazine derivative, photographic characteristics with high sensitivity and ultra-high contrast can be obtained, but since the infectious developability is too strong, in halftone dot image shooting, it is easy to blacken the part that comes out as a white background of the halftone dot, and the result is However, the halftone gradation becomes very short, and the reproducibility of the original document is deteriorated.

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 is required.

As such attempts, for example, Japanese Patent Application Laid-Open No. Sho 61-213847 and Japanese Patent Application Laid-Open No. Sho 62-260153
Hydrazine derivatives disclosed in Japanese Unexamined Patent Publications Nos. 4-13839, Hei 4-13639, and Japanese Unexamined Patent Publication Nos. Hei 4-438, Hei 4-563, Hei 4-6548, Hei 4
A method of adding a redox compound such as a hydroquinone derivative disclosed in JP-A-6551 to a silver halide emulsion layer to release a development inhibitor like a silver image has been known. However, the redox reactivity of these redox compounds tends to depend on the pH of the developing solution, and when processed with a developing solution having a relatively low pH (pH = 11 or less), a super-high contrast image is obtained, -The effects on the reproducibility of Gothic characters and halftone gradation were still insufficient.

[0007] Also in color photographic light-sensitive materials, it is effective to use a redox compound which releases a development inhibitor in order to achieve the objects of improvement in sharpness, granularity and color reproducibility. . However, in recent years, it has been desired to improve photographic properties which are increasingly sophisticated and various, and the conventionally used compounds cannot be sufficiently improved and are unsatisfactory, and further improvements are desired.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide excellent image quality such as sharpness, granularity, resolution and color reproducibility, and a relatively low pH (pH 7.5 or more and less than 10.5).
An object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining a stable and ultra-high contrast image even in processing with a developer. Another object of the present invention is to provide a silver halide photographic light-sensitive material having good reproducibility for Mincho and Gothic characters and a wide halftone reproduction range.

[0009]

The object of the present invention is to provide: (1) a silver halide photographic material having at least one silver halide emulsion layer, which is oxidized by an oxidant of a developing agent to form a development inhibitor; A silver halide photographic material comprising at least one compound that changes. (2) The silver halide photograph described in the above (1), wherein the compound which is oxidized by an oxidized form of the developing agent and changes into a development inhibitor is a compound represented by the following general formula (1). Photosensitive material.

[0010]

Embedded image [In the formula, R, R ′ and R ″ represent a hydrogen atom or a monovalent substituent.) (3) The compound represented by the general formula (1) is converted to a monovalent compound represented by R or R ′ The substituent is a monovalent aromatic ring residue or a heterocyclic residue, and at least one of them has an electron donating group, and the monovalent substituent represented by R ″ is a monovalent substituent. (2) The silver halide photographic material as described in (2) above, which is a compound represented by formula (1), which is a valent aromatic ring residue or a heterocyclic residue. (4) When the compound represented by the general formula (1) is R, R ′,
(2) or (3), wherein at least one of the monovalent substituents represented by R ″ is a compound represented by the general formula (1) having an adsorptive group to silver halide. (5) The silver halide photographic material as described in (4) above, wherein the adsorptive group is an adsorptive group having a thioether structure. Is a compound represented by R, R ',
(2) wherein at least one of the monovalent substituents represented by R ″ is a water-soluble group or a compound represented by the general formula (1) having a water-soluble group as a substituent. A silver halide photographic light-sensitive material according to any one of (1) to (5), wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2). The silver halide photographic light-sensitive material according to any one of the above (2) to (6).

[0011]

Embedded image [Wherein, Y, Y ′ and Y ″ represent monovalent substituents.
m and n represent the integer of 0-5. (8) When the compound represented by the general formula (2) is Y, Y ′,
The halogenation according to the above (7), wherein at least one of the monovalent substituents represented by Y ″ is a compound represented by the general formula (2) having an adsorptive group to silver halide. (9) The silver halide photographic material as described in (8) above, wherein the adsorptive group is an adsorptive group having a thioether structure (10) Formula (2) Compounds are Y, Y ',
At least one of the monovalent substituents represented by Y ″ is a compound represented by the general formula (2), which is a water-soluble group or a substituent having a water-soluble group as a substituent. (7) The silver halide photographic light-sensitive material according to any one of the above (7) to (9) (11) A compound which is oxidized by an oxidized form of a developing agent and changes into a development inhibitor is contained in a photographic constituent layer other than the emulsion layer. The silver halide photographic light-sensitive material according to any one of the above (1) to (10), which is characterized in that the nucleating agent is added.
A silver halide photographic light-sensitive material as described in any one of (1) to (11). (13) The silver halide photographic material as described in (12) above, wherein the nucleating agent is a hydrazine derivative. (14) The silver halide photographic material as described in any one of (1) to (13) above, further comprising a nucleation accelerator. (15) The silver halide photographic material as described in (14) above, wherein the nucleation accelerator is an amine compound. (16) After the imagewise exposure of the silver halide photographic material described in any one of the above (1) to (15), the pH is 7.5.
A method for processing a silver halide photographic light-sensitive material, wherein the development processing is carried out with a developing solution having a content of less than 10.5. (17) A formazan compound represented by the following general formula (3).

[0012]

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. (18) When the compound represented by the general formula (3) is R, R ′,
At least one of the monovalent substituents represented by R ″ is a compound represented by the general formula (3), which is a water-soluble group or a substituent having a water-soluble group as a substituent. (17) A formazan compound represented by the following general formula (4).

[0013]

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.] (20) The compound represented by the general formula (4) , Y, Y ',
At least one of the monovalent substituents represented by Y ″ is a compound represented by the general formula (4), which is a water-soluble group or a substituent having a water-soluble group as a substituent. This is achieved by the formazan compound according to the above (19).

The silver halide photographic light-sensitive material of the present invention comprises p
The effect can be obtained even if the development processing is carried out with a development processing liquid having H of 10.5 or more.
No. 47, JP-A-62-260153, JP-A-4-136839, JP-A-4-438, JP-A-4-563, JP-A-4-6548, JP-A-4-6551 There is a remarkable difference in the effect as compared with a silver halide photographic light-sensitive material using a redox compound disclosed in, for example, Japanese Patent Application Publication No.

Hereinafter, the present invention will be described in detail.

First, the compound used in the present invention, which is oxidized by an oxidized form of the developing agent and changes into a development inhibitor, will be described.

The compound which is oxidized by the oxidized form of the developing agent and changes into a development inhibitor as referred to herein is converted into a compound having a development suppressing ability by being oxidized by the oxidized form of the developing agent, or It refers to a compound that changes to a compound having enhanced development inhibiting power over the original compound.

Therefore, the compound of the present invention which is oxidized by the oxidized form of the developing agent and changes into a development inhibitor is separated by the oxidized form of the developing agent to release the development inhibitor contained in the molecule. Thus, the compound is different from a compound (so-called DIR) which exerts a development suppressing power.

As the compound used in the present invention, which is oxidized by an oxidized form of a developing agent and changes into a development inhibitor, a compound represented by the following general formula (1), and a compound represented by the following general formula (2) Are preferably used.

[0020]

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

[0021]

Embedded image [Wherein, Y, Y ′ and Y ″ represent monovalent substituents.
m and n represent the integer of 0-5. Next, the compound represented by the general formula (1) and the compound represented by the general formula (2) will be 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, a cyano group, an alkenyl group, a hydroxy group, an oxycarbonyl group, an oxyoxalyl group, an acyl group, a sulfonyl group, an amino group, and a mercapto group, which may be further substituted.

Preferred as the monovalent substituent represented by R and R 'are an aromatic or heterocyclic group which may have a substituent.

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, an imidazole residue and the like. 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 according to Hammett's rule. Examples of the electron donating group are an alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group) and an amino group. (For example, dimethylamino group, methylethylamino group) and the like.

In the general formula (2), examples of the monovalent substituent represented by Y, Y ', Y "include halogen (fluorine, chlorine, bromine, iodine), 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 (1),
At least one of the monovalent substituents represented by R, R 'and R ";
One has an adsorptive group to silver halide, or in the compound represented by the general formula (2), at least one of the monovalent substituents represented by Y, Y ′ and Y ″ is When the compound has an adsorptive group to silver, general formulas (1) and (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 the silver halide includes an atom 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 the 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 preferred 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 ″
One or a compound represented by the general formula (2), wherein 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. The reaction at the time of development is faster, and the residual color on the light-sensitive material after development is preferably reduced.The water-soluble group referred to above means a group that can be anionized in a developer, and specifically, Examples thereof include a sulfonamide group, a sulfamoyl group, a phenolic hydroxyl group, a carboxyl group, a sulfo group, and salts thereof, and preferred water-soluble groups are a carboxyl group and a sulfo group.

Next, the formazan compound represented by the following general formula (3) and the formazan compound represented by the following general formula (4) will be described.

[0036]

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. ]

[0037]

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.] In the general formula (3), R, R' and R" As the monovalent substituent represented by the formula: R, in general formula (1),
Examples of the monovalent substituent described in the description of the monovalent substituent represented by R ′ and R ″ include the monovalent substituent. The adsorptive group of the monovalent substituent on silver halide is represented by the general formula ( The adsorbing group to silver halide described in the description of the monovalent substituent represented by R, R 'and R "in 1) can be mentioned.

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), the monovalent substituent represented by Y, Y ', Y "is the same as the one 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 a plurality of monovalent substituents represented by Y, Y 'and Y "are present, 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.

Hereinafter, a compound represented by the general formula (1):
Specific examples of the compound represented by the general formula (2), the formazan compound represented by the general formula (3), and the formazan compound represented by the general formula (4) are shown below. The silver halide photographic light-sensitive material of the present invention is shown below. The compound represented by the general formula (1) and the compound represented by the general formula (2), the formazan compound represented by the general formula (3), and the compound represented by the general formula (4) The formazan compounds represented are not limited to these.

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image <Synthesis of Compound A-8>

[0065]

Embedded image

Compound (2) (3.1 g) is diazotized by a conventional method to synthesize compound (3).

Compound (1) (2.0 g) is dissolved in ice water (10 ml), and 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>

[0068]

Embedded image

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-51 4.
5 g are obtained.

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>

[0073]

Embedded image

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) may be added to any layer provided on the side of the support having the emulsion layer. Can be contained, for example, in the emulsion layer, in the hydrophilic colloid layer adjacent to the emulsion layer, or in the hydrophilic colloid layer provided via the intermediate layer. A particularly preferred layer containing the compound represented by formula (2) or the compound represented by formula (2) is an emulsion layer and / or a hydrophilic colloid layer adjacent to the emulsion layer. A hydrophilic colloid layer is provided between the emulsion layer and the support close to each other, and is added to the hydrophilic colloid layer.

The compound represented by the general formula (1) of the present invention,
The compound represented by the general formula (2) may be contained in a plurality of different layers.

The compound represented by the general formula (1) of the present invention,
Compounds represented by the general formula (2) include alcohols such as methanol and ethanol, glycols such as ethylene glycol, triethylene glycol and propylene glycol, ethers, esters such as dimethylformamide, dimethylsulfoxide, tetrahydrofuran, and ethyl acetate. , Or after dissolving in ketones such as acetone and methyl ethyl ketone. Those hardly soluble in water or an organic solvent can be dispersed and added so as to have an average particle diameter of 0.01 μm to 6 μm by high-speed impeller dispersion, sand mill dispersion, ultrasonic dispersion, ball mill dispersion or the like. For dispersion of the compound represented by the general formula (1) and the compound represented by the general formula (2), an anionic or nonionic surfactant, a thickener, a latex, or the like can be used.

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

The silver halide emulsion layer containing the compound represented by the general formula (1) and the compound represented by the general formula (2) has a silver weight of 0.01 g to 5 g per m ² ,
The gelatin weight is preferably 0.01 g to 5 g, and the value of silver weight / gelatin weight is 0.01 to 20 g.
Is preferably within the range.

Next, the nucleating agent used in the present invention will be described.

The nucleating agent is one that is contained in an emulsion layer, a non-emulsion layer or a developer to promote the formation of metallic silver during the development processing. As a specific example, a hydrazine compound described later, Japanese Patent Publication No.
Quaternary ammonium salts described in Japanese Patent Publication No. 0, JP-B-7-117691 and the like. This nucleating agent does not include hydroquinone derivatives, phenylenediamine derivatives, and phenidone, which are so-called developing agents.

It is preferable to provide a layer containing a nucleating agent in the silver halide photographic light-sensitive material, since the effects of the present invention can be more remarkably exhibited. Further, when the following hydrazine derivatives are used as nucleating agents, the effects of the present invention can be further remarkable.

The hydrazine derivative used as a nucleating agent in the present invention is a compound represented by the following formula (H).

[0083]

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, each substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, heterocyclic group, hydroxyl group, alkylthio group, hydrazino group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino group , A carbamoyl group or an oxycarbonyl group. ]

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

[0085]

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 on 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 formula (Ha), R ²⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl 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. ).

The specific examples of the compound represented by formula (H) are shown below, but the compounds represented by formula (H) that can be used in the present invention are not limited thereto.

[0093]

Embedded image

[0094]

Embedded image

[0095]

Embedded image

[0096]

Embedded image

[0097]

Embedded image

[0098]

Embedded image

[0099]

Embedded image

[0100]

Embedded image

Specific examples of other preferable 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 preferred that the layer having the largest silver / gelatin ratio in the emulsion layer contains at least one hydrazine derivative. 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 that makes it harder (a higher contrast amount).

[0106] 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 any layer in any state.

Next, the nucleation accelerator used in the present invention will be described.

The nucleating accelerator, when used simultaneously with the above-mentioned nucleating agent, promotes the formation of metallic silver during the development process by including it in an emulsion layer, a non-emulsion layer or a developer. A thing. As specific examples, JP-A-60-140340, JP-A-61-47945, JP-A-61-47924, and JP-A-62-2
50439, JP-A-62-280733,
Examples thereof include amine compounds and onium compounds described in JP-A-1-179930, JP-A-2-2542, and JP-A-4-62544.

It is preferable to provide a layer containing a nucleation accelerator in the silver halide photographic light-sensitive material because sensitivity and γ (gamma) can be increased. Further, when the following amine compound is used as a nucleation accelerator, sensitivity and γ can be further increased.

The amine compound used as a nucleation accelerator in the present invention is preferably a compound represented by the following formula [Na].

[0112]

Embedded image

In the above general formula [Na], R ¹¹ ,
R ¹² and R ¹³ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, each of which may be further substituted. Further, R ¹¹ , R ¹² and R ¹³ may form a ring together.

Particularly preferred amine compounds are aliphatic tertiary amine compounds.

These amine compounds preferably have a diffusion-resistant group or a silver halide adsorbing group in the molecule.

In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is more preferable. Preferred examples of the silver halide adsorption group include a heterocyclic ring, a mercapto group, a thioether group, a thione group, and a thiourea group.

Particularly preferred as the compound represented by the general formula [Na] is a compound having at least one thioether group as a silver halide adsorbing group in the molecule.

Specific examples of the amine compound represented by the general formula [Na] are shown below, but the amine compound represented by the general formula [Na] which can be used in the present invention is not limited thereto. Absent.

[0119]

Embedded image

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image

[0123]

Embedded image

In the silver halide photographic light-sensitive material, 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.

The silver halide grains were converted into spheres of the same volume,
The converted sphere diameter is the particle diameter 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.

The shape of the silver halide grains is not limited.
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 one of a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. A method of forming grains in the presence of excess silver ions (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.

The silver halide grains are formed in at least one of the steps of forming or growing the grains, such as cadmium salts, zinc salts, lead salts, thallium salts, ruthenium salts, osmium salts, iridium salts, rhodium salts, or salts thereof. 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, formamidine sulfinic acid, silane compounds and the like.

The silver halide emulsion may be spectrally sensitized to a desired wavelength by 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, and 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, those described in the specification;
Compounds represented by the general formula [1] described on page 3 of Japanese Patent Application No. 5-129157 (as specific examples, for example, 1-1 to 1-57 on page 17 to 22), and Compounds represented by the general formula [2] described on page 4 (specific examples include:
For example, 2-1 to 2-48 described on pages 23 to 34),
Compounds represented by the general formula [3] described on pages 4 to 5 (specific examples include, for example, 3-1 described on pages 35 to 48).
To 3-48), a compound represented by the general formula [1] described on page 3 of Japanese Patent Application No. 5-129158 (as specific examples, for example, 1-1 to -14 described on pages 14 to 16). 1-1
4), a compound represented by the general formula [2] described on page 4 (specific examples include, for example, 2
-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, issued in 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 3,46.
9,987, 3,425,835,
No. 3,342,605, British Patent No. 1,27
1,329, 1,038,029,
No. 1,121,174, US Pat. No. 3,663
There is a method described in JP-A Nos. 0,101 and 3,658,546. 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, 17643 (19).
(Issued December, 1978), page 23, IV, 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 coating aid, antistatic property, improvement of slipperiness, emulsification / dispersion, prevention of adhesion and improvement of 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 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 which releases a photographically useful compound upon being oxidized is gelatin, in order for the compound to be oxidized, the layer must be 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 poorly 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 No. 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 subjected to imagewise exposure 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 developing 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.

It is preferable to add a preservative 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 viscous liquid in a semi-kneaded state having a high viscosity, as a mixture of solid components, an organic aqueous solution containing glycol or amine. 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 development is performed by processing in an aqueous alkali solution. 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 (eg, sulfite or bisulfite), a pH buffer (eg, acetic acid), a pH adjuster (eg, sulfuric acid), a chelating agent capable of softening water. A compound such as an agent can be included.

The silver halide photographic 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 carried out 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 shortening 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 to
Dry time. Preferred total processing time (Dry to Dry)
Is 15 to 50 seconds.

The automatic developing machine is provided with a heat transfer material of 90 ° C. or higher (for example, a heat roller of 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.

When the silver halide photographic light-sensitive material of the present invention is a silver halide color photographic light-sensitive material, at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer of a silver halide emulsion layer is provided on a support. One layer is provided. Further, a non-photosensitive layer can be provided on the silver halide color photographic material. The number and order of the silver halide emulsion layer and the non-light-sensitive layer are not particularly limited.

One example of a silver halide color photographic light-sensitive material has, on a support, a light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. It is a silver halide photographic material. The photosensitive layer having substantially the same color sensitivity may be a photosensitive layer having color sensitivity to any of blue light, green light, and red light. Another example is a multi-layer silver halide color photographic light-sensitive material, which has a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. The red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer are generally provided in the order of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer in order from the support side. I have. However, depending on the purpose, the above-mentioned arrangement order may be reversed, or the arrangement order may be such that layers having different photosensitivity are sandwiched between layers having the same color sensitivity.

[0177]

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 7 g Nitric acid 5% 6.5 ml K ₂ RhCl ₅ (H ₂ O) 0.06 mg ion exchange water 700 ml D solution: silver nitrate 154 g nitric acid 5% 4.5 ml ion exchange water 200 ml E solution: 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, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was 1.5 × 10 ^-3 mol and potassium bromide 8.5 ×, 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) A 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 >> On one side of the undercoated support, a redox compound layer, a solid disperse dye layer, and a silver halide emulsion layer each having the following formulation from the support side , The intermediate layer and the emulsion protective layer are simultaneously coated in layers, cooled and set, and then the backing layer and the backing protective layer composed of the following formula are simultaneously coated from the support side on the opposite side of the undercoated support. Then -1
The sample was cooled and set at ℃, and both surfaces were simultaneously dried to prepare a sample 101.

<Redox compound layer> Silver halide emulsion A-2 Ag amount 0.3 g / m ² Gelatin 0.3 g / m ² Saponin 60 mg / m ² Comparative 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) 0.3 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-29 10 mg / m ² Polymer latex L-1 (average grain 0.5 g / m ² colloidal silica 75% by weight, 12.5% by weight of vinyl acetate, 12.5% by weight of vinyl pivalinate suspension polymer 1.0 g / m ² Nin 20 mg / m ² 2-mercapto-6-hydroxypurine 2 mg / m ² Ascorbic acid 20 mg / m ² EDTA · 2Na 25 mg / m ² Sodium polystyrene sulfonate (average molecular weight 500,000) 15 mg / m ² It was 2.

<Intermediate layer> Gelatin 0.32 g / m ² nucleation accelerator: amine compound Na-3 12.9 mg / m ² Polymer latex L-1 (average particle size 0.10 μm) 0.3 g / m ² polystyrene Sodium sulfonate (average molecular weight 500,000) 10mg / m ²

<Emulsion protective layer> Gelatin 0.48 g / m ² Water-soluble dye F-2 50 mg / m ² Sodium-iso-amyl-n-decyl sulfosuccinate 12 mg / m ² Compound SA-1 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 45 mg / m ^{2 having an} average particle diameter of 3 μm sodium-di (2-ethylhexyl) sulfosuccinate 10 mg / m ²

<< Silver halide photographic light-sensitive material sample 102-
Preparation of 134 >> Comparative compound of redox compound layer T-
Samples 102 to 134 were produced in the same manner as in Sample 101 except that 1 (compound) was changed as shown in Tables 1 and 2.

<< Evaluation of Samples >> Samples 101 to 13 Obtained
For 4, the sensitivity and γ were measured as follows, and
The eye-drawing performance was evaluated. Table 1 and Table 2 show the obtained results.
Shown in

In the measurement of the sensitivity and γ and the 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 15 ° C. 20 seconds Squeeze / Dry 45 ° C. 30 seconds 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.

(Developer 2) The developer 2 was adjusted in the same manner as the developer 1, except that the amount of KOH was changed so that the pH of the working solution was 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, pure water 6
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.

A completely crushed one is defined as a 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.

[0205]

[Table 1]

[0206]

[Table 2]

[0207]

Embedded image

From the results shown in Tables 1 and 2, the samples using the compounds of the present invention exhibited high sensitivity and high γ even when developed using a developing solution having a pH of 10.5 or less. It can be seen that the stretching performance is good. By introducing an adsorbing group, improvement of the enlargement performance is seen,
In particular, when the adsorptive group is a thioether group, it can be seen that the stretching 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.

[0210]

Embedded image

[0211]

Embedded image

[0212]

Embedded image

Example 2 (Preparation of Silver Halide Emulsion B-1) Using a double jet method, 70 mol% of silver chloride was used, and the remainder was made of 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 sodium chloride.
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.

To the resulting emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 1.5 × 10 ^-3 mol per mol of silver, and potassium bromide was added in an amount of 8.5 × 10 3.
^-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 S-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 light-sensitive material sample 201 >> On one side of the support, a gelatin undercoat layer of the following formulation 1 from the support side, a silver halide emulsion layer 1 of the following formulation 2,
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 Comparative 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 of 1.5 g / m ² equivalent Sensitizing dye S-3 150 mg / Ag 1 mol Hydrazine compound H-26 2 × 10 ^-3 Mol / Ag 1 mol Amino compound Na-3 7 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- decyl sulfosuccinate 0.7 mg / m ² sodium naphthalene sulfonate 8 mg / m ² saponin 20 mg / m ² hydroquinone 20 mg / m ² 2-mercapto-6-hydroxy purine 2mg / 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 coating solution pH was 5.2.

Formulation 3 (Silver Halide Emulsion Layer 2) Silver Halide Emulsion B-2 Amount of silver equivalent to 1.5 g / m ² Sensitizing dye S-4 100 mg / Ag 1 mol Hydrazine compound H-27 4 × 10 ^-3 Mol / Ag 1 mol Amino compound Na-3 7 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 1.7 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 0.05 .mu.m) 150 mg m ² gelatin coating solution pH using phthalated gelatin 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 12 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-1 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 size 0.10 μm) 0.25 g / m ² colloidal silica (average particle size 0.05 μm) 500 mg / m ² dye F-6 20 mg / m ² 1,3-vinyl Sulfonyl-2-propanol 40 mg / m ² Hardener K-1 30 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Fungicide 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 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 234 >> Comparative compound of gelatin undercoat layer T-1
Samples 202 to 234 were produced in the same manner as in Sample 201 except that (compound) was changed as shown in Tables 3 and 4.

<< Evaluation of Samples >> Samples 201 to 23 Obtained
For 4, the sensitivity and γ were measured as follows, and
The halftone was evaluated. Tables 3 and 4 show 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 15 ° C. 20 seconds Squeeze / dry 50 ° C. 30 seconds Total 100 seconds

(Developer) Per liter of working solution diethyltriaminepentaacetic 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.

(Composition of fixing solution) 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.

[0232] exposure <sensitivity measurement of gamma> is a laser sensitometer using a He-Ne laser with a wavelength of 633nm as a light source, performs the step exposure while light amount change by 1.5 × 10 ^-7 seconds, the automatic developing machine 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.

[0237]

[Table 3]

[0238]

[Table 4]

From the results shown in Tables 3 and 4, the samples using the compounds of the present invention exhibited high sensitivity and high γ 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 halftone reproduction range can be obtained.
The halftone reproduction range is improved by introducing the adsorptive group. In particular, when the adsorbing group is a thioether group, the halftone reproduction range is improved while maintaining high sensitivity.

[0240]

Embedded image

[0241]

Embedded image

Example 3 << Preparation of Multilayer Color Photosensitive Material Sample 301 >> Each layer having the following composition was sequentially applied to a subbed triacetyl cellulose film support from the support side to prepare a multilayer color photosensitive material sample 301. . The coating amount of each component is shown per 1 m ² . Silver halide and colloidal silver are shown in terms of silver amount. First layer (antihalation layer) Ultraviolet absorber U-1 0.3 g Ultraviolet absorber U-2 0.4 g High boiling point solvent O-1 1.0 g Black colloidal silver 0.24 g Gelatin 2.0 g Second layer (intermediate) Layer) 2,5-di-t-octylhydroquinone 0.1 g High-boiling solvent O-1 0.2 g Gelatin 1.0 g Third layer (low-sensitivity red-sensitive silver halide emulsion) Red sensitizing dye (S-1, AgBrI spectrally sensitized by S-2) (AgI 4.0 mol%, average particle size 0.25 μm) 0.5 g Coupler C-1 0.1 mol High boiling solvent O-2 0.6 g Gelatin 1.3 g

Fourth Layer (High-Sensitivity Red-Sensitive Silver Halide Emulsion) AgBrI (AgI 2.0 mol%, average particle diameter 0.6 μm) spectrally sensitized by a red sensitizing dye (S-1, S-2) 0.8 g Coupler C-1 0.2 mol High boiling solvent O-2 1.2 g Gelatin 1.8 g Fifth layer (intermediate layer) 2,5-di-t-octylhydroquinone 0.1 g High boiling solvent O- 1 0.2 g Gelatin 0.9 g Sixth layer (low-sensitivity green-sensitive silver halide emulsion) AgBrI (AgI 4.0 mol%, averaged) spectrally sensitized by green sensitizing dyes (S-3, S-4) 0.6 g coupler C-2 0.04 mol coupler C-3 0.01 mol high boiling point solvent O-3 0.5 g redox compound T-1 0.02 g gelatin 1.4 g 7th layer ( High sensitivity green-sensitive silver halide emulsion) AgBrI spectrally sensitized by green sensitizing dyes (S-3, S-4) (AgI 2.0 mol%, average particle size 0.6 μm) 0.9 g Coupler C-2 0.10 mol Coupler C-3 0.02 mol High boiling solvent O-3 1.0 g Gelatin 1.5 g

Eighth layer (intermediate layer) 2,5-di-t-octylhydroquinone 0.1 g High boiling point solvent O-1 0.2 g Gelatin 0.9 g Ninth layer (yellow filter layer) Yellow colloidal silver 0.1 g Gelatin 0.9 g 2,5-di-t-octylhydroquinone 0.1 g High-boiling solvent O-1 0.2 g 10th layer (low-sensitivity blue-sensitive silver halide emulsion) Spectroscopy with blue sensitizing dye (S-5) Sensitized AgBrI (AgI 4.0 mol%, average particle size 0.35 μm) 0.6 g Coupler C-4 0.3 mol High boiling solvent O-3 0.6 g Gelatin 1.3 g 11th layer (high sensitivity) Blue-sensitive silver halide emulsion) AgBrI spectrally sensitized with a blue sensitizing dye (S-5) (AgI 2.0 mol%, average particle size 0.9 μm) 0.9 g Coupler C-4 0.5 mol High Boiling solvent -3 1.4 g gelatin 2.1 g 12th layer (first protective layer) UV absorber U-1 0.3 g UV absorber U-2 0.4 g high boiling point solvent O-3 0.6 g gelatin 1.2 g 2 , 5-Dioctylhydroquinone 0.1g

Thirteenth Layer (Second Protective Layer) Average grain size (r) 0.08 μm Non-photosensitive fine grain silver halide emulsion composed of silver iodobromide containing 1 mol% of silver iodide Silver amount 0.3 g Polymethyl Methacrylate particles (1.5 μm in diameter) 0.05 g Surfactant-1 0.015 g Gelatin 0.7 g To each layer, in addition to the above composition, gelatin hardener-1 and a surfactant were added. Tricresyl phosphate was used as a solvent for the coupler.

[0246]

Embedded image

[0247]

Embedded image

[0248]

Embedded image

[0249]

Embedded image

<< Multilayer Color Photosensitive Material Samples 302 to 306 >>
Preparation of Samples 302 to 306 were prepared in the same manner as Sample 301 except that the redox compound T-1 (compound) in the sixth layer was changed as shown in Table 5.

<Evaluation of Samples><Measurement of Sensitivity and γ> The obtained samples 301 to 306 were exposed to sensitometry and developed under the following processing conditions.

(Processing conditions) Processing step Processing time Processing temperature First development 6 minutes 38 ° C. Rinse 2 minutes 38 ° C. Inversion 2 minutes 38 ° C. Color development 6 minutes 38 ° C. Adjustment 2 minutes 38 ° C. Bleaching 6 minutes 38 ° C. Fixing 4 minutes 38 C. Water washing 4 minutes 38.degree. C. Stable 1 minute 15.degree.

(First developer) Sodium tetrapolyphosphate 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2 g Potassium bromide 2 0.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Add water to 1000 ml

(Reversal solution) Nitrilotrimethylenephosphonic acid · 6 sodium salt 3 g Stannous chloride (dihydrate) 1 g p-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 mL Add water to 1000 mL

(Color developing solution) Sodium tetrapolyphosphate 3 g Sodium sulfite 7 g Sodium tertiary phosphate (dihydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90 ml Sodium hydroxide 3 g Citrazinic acid 1.5 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amino aniline / sulfate 11 g 2,2-ethylenedithiodiethanol 1 g Add water to 1000 ml

(Preparation liquid) Sodium sulfite 12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerin 0.4 mL Glacial acetic acid 3 mL Add water 1000 mL

(Bleaching solution) Sodium ethylenediaminetetraacetate (dihydrate) 2 g Iron (III) ammonium ethylenediaminetetraacetate (dihydrate) 120 g Ammonium bromide 100 g Water was added to 1000 ml.

(Fixing solution) Ammonium thiosulfate 80 g Sodium sulfite 5 g Sodium bisulfite 5 g Water was added to 1000 ml.

(Stabilizing Solution) Formalin (37% by weight) 5 ml Conidax (manufactured by Konica Corporation) 5 ml Water was added to 1000 ml. The density of the developed sample was measured through a green filter to obtain a photographic characteristic curve.

The reciprocal of the exposure amount giving a density of 0.5 was defined as the sensitivity, and the sensitivity of each sample was determined by relative sensitivity with the sensitivity of the sample 301 being 100.

The tangent of a straight line connecting the point of density 0.2 and the point of density 1.2 of the photographic characteristic curve was defined as γ.

<Measurement of RMS and CTF> Sample 3 obtained
After exposing Nos. 01 to 306 through a filter having a stepwise changing density, development processing was performed under the above processing conditions.

The granularity (RMS) was measured using a green filter. The granularity was measured by a conventional RMS method at a density of 1.0 part. An aperture having a diameter of 48 μm was used as an aperture for measurement.

Further, the CTF was measured using a microphotometer.
Was measured.

Table 5 shows the obtained results.

[0266]

[Table 5]

From the results shown in Table 5, the sample using the compound of the present invention was represented by the RMS value despite that the same sensitivity and γ were obtained as the sample 301 using the comparative compound (T-1). It can be seen that the granularity is long. In addition, it is understood that the value of CTF is larger than that of the comparative sample, and the sharpness is improved.

Example 4 << Preparation of silver halide photographic light-sensitive material sample 401 >> In preparation of silver halide photographic light-sensitive material sample 201 of Example 2, the gelatin undercoat layer of Formula 1 was prepared by using gelatin A silver halide photographic material 201 was prepared in the same manner as in the silver halide photographic light-sensitive material sample 201 except that the silver halide emulsion layer 1 was replaced with the silver halide emulsion layer 1 having the following formulation 2. Photographic material sample 401 was prepared.

Formulation (Gelatin undercoat layer) Gelatin 0.45 g / m ² Saponin 56.5 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 (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 Comparative compound T-1 (dissolved in ethyl acetate After dispersing in a gelatin solution, ethyl acetate was removed under reduced pressure to precipitate in the form of solid fine particles.) 25 mg / m ² Hydrazine compound H-26 2 × 10 ^-3 mol / Ag 1 mol Amino compound Na-3 7 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 -Decyl sulfosuccinate 0.7 mg / m ² sodium naphthalene sulfonate 8 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 0.05 μm) 150 mg / m ² Ascorbic acid 20 mg / m ² EDTA 25 mg / m ² Sodium polystyrene sulfonate 15 mg / m ² Coating solution pH Was 5.2.

<< Silver halide photographic light-sensitive material sample 402-
Preparation of 434 >> Comparative compound T of silver halide emulsion layer 1
Samples 402 to 417 were produced in the same manner as in Sample 401, except that -1 (compound) was changed as shown in Tables 6 and 7.

<< Evaluation of Samples >> Samples 401 to 43 Obtained
For No. 4, the sensitivity and γ were measured in the same manner as in Example 2, and the halftone was evaluated. Note that the sensitivity was measured in Example 2.
The relative values are shown with the sensitivity of Sample 201 being 100. Tables 6 and 7 show the obtained results.

[0273]

[Table 6]

[0274]

[Table 7]

From the results shown in Tables 6 and 7, it can be seen that high sensitivity, high γ and an image having a wide halftone reproduction range can be obtained even in the sample containing the compound of the present invention in the emulsion layer. Recognize.

The compounds used in the following Examples 5 to 9 are shown below.

[0277]

Embedded image

[0278]

Embedded image

[0279]

Embedded image

[0280]

Embedded image

[0281]

Embedded image

[0282]

Embedded image

The compounds of the present invention and comparative compounds dr-1 and dr-2 used in the following Examples 5 to 9 were added in the following addition modes. (Oil dispersion) (Displayed as “oil” in the form of addition) 5 g of the compound of the present invention or 5 g of each of the comparative compounds was added to a mixed solvent consisting of 10 g of tricresyl phosphate (a high-boiling organic solvent) and 5 g of ethyl acetate. Each time, it was heated and dissolved to prepare a solution.

The above solution was prepared by adding 2 g of gelatin to 200 cc of water.
And 0.1 g of the following surfactant was added thereto, mixed at a stretch in an aqueous solution kept at 40 ° C., subjected to ultrasonic dispersion while stirring, and completely dispersed to prepare an oil dispersion.

[0285]

Embedded image

(Acid precipitation) (addition form is indicated as "acid precipitation") 6 g of each of the compound of the present invention or the comparative compound was added to 200 ml of a 2% gelatin aqueous solution containing 0.002% of the above surfactant.
And the pH is adjusted to 1 by adding an aqueous solution of sodium carbonate.
It was raised to 0.2 and dissolved. While sufficiently stirring the obtained solution, citric acid was added dropwise, the pH was lowered to 5.6, and the solution was precipitated to prepare an acid precipitation dispersion.

(Preparation of solid dispersion) (Form of addition "solid")
To each 1 g of the compound of the present invention or the comparative compound, 0.01 g of the above surfactant was added, 90 cc of water was added, and the mixture was dispersed with a planetary ball mill using zirconia beads having a particle diameter of 1 mm to obtain a solid dispersion. It was adjusted.

(Methanol solution) (Addition form is shown as "methanol") 2 g each of the compound of the present invention or the comparative compound was dissolved in 100 cc of methanol to prepare a methanol solution.

Example 5 (Preparation of silver halide emulsion C-1) K ₃ Rh (NO)
₄ (H ₂ O) ₂ was added to 7 moles per mole of silver at the end of grain formation.
× 10 ⁻⁸ mol, K ₃ OsCl ₆ in the presence of 8 × 10 ⁻⁶ mol, 40 ° C., pH 3.0, silver potential (EAg) 165 mV
While keeping the above conditions, an aqueous silver nitrate solution and a water-soluble halide solution were mixed at the same time to prepare silver chlorobromide core particles having an average diameter of 0.09 μm comprising silver chloride of 70 mol% and the remainder being silver bromide.

The EAg was then reduced to 125 mV with sodium chloride and the silver chlorobromide core particles were shelled using a double jet method. At this time, K ₂ IrCl ₆ was added to the halide solution as silver 1
3 × 10 ^-7 mol and 9 × 10 ^-8 mol of K ₃ RhCl ₆ were added per mol. Further, KI conversion was performed using silver iodide fine particles. The resulting emulsion had an average diameter of 0.15μ.
m / core / shell type monodisperse (coefficient of variation: 10%) cubic silver chloroiodobromide (70 mol% silver chloride, 0.2 mol% silver iodobromide, silver bromide balance). .

Next, modified gelatin described in JP-A-2-280139 (substituted by substituting phenylcarbamyl for an amino group in gelatin, Exemplified Compound G-8 described in JP-A-2-280139, page 287 (3)). ) To desalinate. The EAg after desalting was 190 mV at 50 ° C.

To the resulting emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 15.times.10.sup.- ³ mol per mol of silver, and potassium bromide was added in an amount of 8.times.8 per mol of silver. 5 × supplemented with 10 ^-4 mol, pH 5.6 and further addition of citric acid, prepared in EAg123mV, p-toluenesulfonyl chloro amide sodium trihydrate (chloramine T) per mole of silver 1 × 10 ^- After reacting by adding ³ moles, a solid-dispersed inorganic sulfur (S ₈ ) compound (Seisin Enterprise Co., Ltd .; PM-1200 dispersed to an average of 0.5 μm using saponin) was added in an amount of 1 per mole of silver. .7x1
0 ^-6 mol and chloroauric acid were added per mol of silver 1.5 × 10 ^-5 mol, chemically ripened until maximum sensitivity is obtained at a temperature 55 ° C.. Then, at a temperature of 50 ° C., 5 mg of a sensitizing dye, trihexylamine, per mol of silver was added, and the temperature was further lowered to 40 ° C., followed by 4-hydroxy-6-methyl-1,3,3.
a, 7-Tetrazaindene was used in an amount of 2 × 10 ^-3 mole per mole of silver, and 1-phenyl-5-mercaptotetrazole was used as silver 1 mole.
After adding 3 × 10 ^-4 mole per mole and 5 × 10 ^-3 mole of potassium iodide per mole of silver, the pH was increased to 5.1 with citric acid.
To prepare silver halide emulsion C-1.

(Preparation of Silver Halide Emulsion C-2) The reaction temperature was raised to 50 ° C. to give an average grain size of 0.19 μm, and the amount of K ₃ RhCl ₆ used in forming the shell portion was changed per mole of silver. Silver halide emulsion C except that the amount was 6 × 10 ^-8 mol
In the same manner as in Preparation No.-1, silver halide emulsion C-2 was prepared.

The silver halide emulsion C-2 has 40% higher sensitivity than the silver halide emulsion C-1.

(Preparation of silver halide photographic light-sensitive material)
On one side of the support provided with the layer, the amount of silver was 0.3 g / m 2.^Two, Ze
0.5g / m of latin^Two Halogen of the following formula 1
Silver halide emulsion layer 1, gelatin amount 7.0 g / m^TwoAnd below
Gelatin intermediate layer of formula 2, silver amount 1.6 g / m^Two, Zera
1.4 g / m^TwoHalogenation of the following formula 3
Silver emulsion layer 2, gelatin amount 7.0 g / m^TwoThe following process
Curtain coating so that the protective layer of side 4 is formed in this order.
Simultaneous multi-layer coating at 200m / min speed using a cloth method
After the setting, the amount of gelatin was set to 0. 0 on the opposite side of the support.
8g / m^TwoBacking layer of the following formula 5, gelatin
0.8 g / m^TwoBacking protection of formula 6 below
In order for the layers to be formed in this order, 2
Simultaneous multilayer coating at a speed of 00m / min, cooling at -1 ° C
Set and dry both sides at the same time, silver halide photographic exposure
Material samples 501 to 533 were obtained.

Formulation 1 (Silver Halide Emulsion Layer 1) Silver Halide Emulsion C- ² Equivalent amount of silver 0.3 g / m ² Sensitizing dye; d-1 150 mg / Ag 1 mol Hydrazine compound; H-6 3 mg / m ² amine compound; Na-21 7 mg / m ² Compound a 100 mg / m ² 2-pyridinol 1 mg / m ² Polymer latex; L1 (average particle size 0.25 μm) 0.25 g / m ² Hardener; h1 5 mg / m ² sodium-iso-amyl-n-decylsulfosuccinate 0.7 mg / m ² sodium naphthalenesulfonate 8 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 of ascorbic acid ^{20mg / m 2 EDTA 25mg / m} 2 of polystyrene sulphonic acid sodium The amount the coating solution pH shown in Table 8 in addition form shown in the present invention compound or comparative compound in Table 8 shown in 15 mg / m ² Table 8 was 5.2.

Formulation 2 (Gelatin Intermediate Layer) Gelatin 1.0 g / m ² Saponin 80 mg / m ² Sodium polystyrene sulfonate (average molecular weight 500000) 15 mg / m ² Fungicide Z 0.5 mg / m ² Solid disperse dye; K 7 0.5 mg / m ²

Formulation 3 (Silver Halide Emulsion Layer 2) Silver Halide Emulsion C-1 Silver amount 1.5 g / m ² equivalent Sensitizing dye; d-2 150 mg / Ag 1 mol Hydrazine compound; H-6 15 mg / m ^2- amine compound; Na-21 35 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 1.7 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; L2 (Example 3 in JP-A-5-66512) type Lx -3 composition (9)) 0.25g / m ² colloidal silica (average particle size 0.05 .mu.m) 150 mg / Ag1 mode PH of the coating solution amount gelatin using phthalated gelatin emulsion layer Gal 25 wt% as shown in Table 8 in addition form shown in the present invention compound or comparative compound in Table 8 are shown in Table 8 4. It was 8.

Formulation 4 (Emulsion protective layer) Gelatin 0.7 g / m ² sodium-iso-amyl-n-decylsulfosuccinate 12 mg / m ² matting agent; spherical polymethyl methacrylate having an average particle size of 3.5 μm 25 mg / m ² matting agent; amorphous silica having an average particle size of 8 μm 12.5 mg / m ² surfactant; S1 26.5 mg / m ² sliding agent (silicone oil) 4 mg / m ² Compound a 50 mg / m ² polymer latex; L3 ( 0.25 g / m ² colloidal silica (average particle size 0.05 μm) 150 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Hardener; h2 30 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Fungicide Z 0.5 mg / m ²

Formulation 5 (backing layer composition) Gelatin 1.5 g / m ² sodium-iso-amyl-n-decylsulfosuccinate 5 mg / m ² polymer latex; L3 (average particle size 0.10 μm) 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; f1 65 mg / m ² dye; f2 15 mg / m ² dye; f3 100 mg / m ² 1-phenyl-5 - mercaptotetrazole 10 mg / m ² hardener; h3 100mg / m ² zinc hydroxide ^{50mg / m 2 EDTA 50mg / m} 2

Formulation 6 (Backing protective layer) Gelatin 0.8 g / m ² matting agent; monodispersed polymethyl methacrylate 50 mg / m ² matting agent having an average particle size of 5 μm; amorphous silica 12.5 mg / m ² having an average particle size of 3 μm Sodium-di (2-ethylhexyl) -sulfosuccinate 10 mg / m ² surfactant; S1 1 mg / m ² dye; f1 65 mg / m ² dye; f2 15 mg / m ² dye; f3 100 mg / m ² Compound a 50 mg / m ² hardener; h2 20 mg / m ² sodium polystyrenesulfonate 10 mg / m ²

The obtained sample was subjected to 1.5 × by a laser sensitometer using a 633 nm He—Ne laser as a light source.
The step exposure is performed by changing the amount of light in 10 ^-7 seconds, and an automatic developing machine GR-27 is used using a developing solution and a fixing solution having the following compositions.
(Konica Corporation) under the following conditions. The blackening density of the obtained developed sample was measured with a PDA-65 (Konica Digital Densitometer).

In order to evaluate the reproducibility of minute halftone dots of the obtained sample, small points (5% halftone dots) and midpoints (50% halftone dots) were determined at 3,600 dpi / 300 lpi using SelectSet 5000 manufactured by Agfa. Dots), large dots (95% of dots),
Solid (100% halftone dots) was set to be output, exposure was performed while changing the amount of light, and the same processing was performed. The halftone% of the obtained developed sample was measured with X-Rite361T.

(Composition of developer) Per liter of working solution: diethyltriamine pentaacetic acid / pentasodium salt 1.45 g Dimezone S 0.85 g sodium sulfite 42.5 g potassium sulfite 17.5 g potassium carbonate 55 g hydroquinone 20 g 1-phenyl-5- Mercaptotetrazole 0.03 g Potassium bromide 2.67 g Benzotriazole 0.21 g Boric acid 8 g Diethylene glycol 40 g 8-Mercaptoadenine 0.07 g KOH was added in such an amount that the working solution became pH 10.4.

(Fixing solution composition) Ammonium thioate (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 The pH of the used solution was adjusted to 4.9 with 0 g of aluminum sulfate (27% aqueous solution) and 25 ml of sulfuric acid.

(Processing Conditions) (Step) (Temperature) (Time) Development 35 ° C. 30 seconds Fixing 35 ° C. 20 seconds Water 15 ° C. 20 seconds Squeeze / Drying 50 ° C. 30 seconds Total 100 seconds

(Sensitivity) The logarithm of the reciprocal of the exposure amount giving a blackening density of 1.0 was determined, and expressed as a relative sensitivity with the sensitivity of sample 529 being 100.

(Γ) The logarithm of the reciprocal of the exposure at which the density of 0.05 was obtained is E (0.05), and the log of the reciprocal of the exposure at which the density of 2.5 was obtained is E (2. As 5), γ was determined by the following equation.

Γ = 2.45 / (E (0.05) −E (2.5))

(Evaluation method of dot reproducibility of small dot) Small dot (target dot% 5%) at an exposure amount giving a solid density of 5.0
% Of the dot actually reproduced on the sample was determined. The closer to 5%, the better.

(Method of Evaluating Reproducibility of Halftone Halftone) The halftone point (target halftone 50%) at an exposure amount giving a solid density of 5.0
%), Which was actually reproduced on the sample. 50%
The closer to, the better.

(Residual color) The unexposed sample was processed
Five samples were stacked and the sample containing no the compound of the present invention or the comparative compound was 5. The level where the residual color was extremely badly unworthy of evaluation was 1. The level which was not practically usable was 2. The one which was barely practical level. A visual relative evaluation was performed in a five-step evaluation of 3

Table 8 shows the obtained results.

[0314]

[Table 8]

[0315]

Embedded image As is clear from Table 8, the silver halide photographic light-sensitive material of the present invention has good reproducibility of fine halftone dots.

Example 6 Using the emulsion described in Example 5, according to Example 5, silver halide photographic material samples 601 to 601 having the following three layers were prepared.
607 was created.

(Solid disperse dye layer) Gelatin 0.7 g / m ² Saponin 80 mg / m ² Sodium polystyrene sulfonate (average molecular weight 500000) 15 mg / m ² Fungicide Z 0.5 mg / m ² Solid disperse dye; K7. 5 mg / m ^{2 The} compound of the present invention or the comparative compound shown in Table 9 The amount shown in Table 9 in the form of addition shown in Table 9

(Emulsion Layer) Silver Halide Emulsion C-1 Silver amount 3.2 g / m ² equivalent Sensitizing dye; d-2 150 mg / Ag 1 mol Sodium-iso-amyl-n-decylsulfosuccinate 1.7 mg / M ² Styrene-maleic acid copolymer (molecular weight 70,000) 10 mg / m ² polymer latex; L2 (Japanese Unexamined Patent Publication No. 5-66512, Example 3, type Lx-3 composition (9)) 0.35 g / m ² colloid Silica (average particle size: 0.05 μm) The gelatin amount of the 150 mg / m ² emulsion layer was 1.5 g / m ² , and the pH of the coating solution was 4.8.

(Protective layer) Gelatin 0.7 g / m ² sodium-iso-amyl-n-decylsulfosuccinate 12 mg / m ² matting agent; spherical polymethyl methacrylate having an average particle size of 3.5 μm 25 mg / m ² matting agent Amorphous silica having an average particle size of 8 μm 12.5 mg / m ² surfactant; S1 26.5 mg / m ² slip agent (silicone oil) 4 mg / m ² compound a 50 mg / m ² polymer latex; L3 (average particle size) 0.15 μm) 0.25 mg / m ² colloidal silica (average particle size 0.05 μm) 150 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Hardener; h2 30 mg / m ² polystyrene sulfonic acid Sodium 10 mg / m ² Fungicide Z 0.5 mg / m ²

The obtained sample was exposed and treated in the same manner as in Example 5.
Processing, by the following, sensitivity, γ, halftone dot reproducibility,
The residual color was evaluated.

(Sensitivity) The logarithm of the reciprocal of the exposure amount giving the blackening density of 3.0 was determined, and expressed as a relative sensitivity with the sensitivity of sample 607 being 100.

(Γ) The logarithm of the reciprocal of the exposure amount at which the density of 0.05 was obtained is E (0.05), and the logarithm of the reciprocal of the exposure amount at which the density of 2.5 was obtained is E (2. As 5), γ was determined by the following equation.

Γ = 2.45 / (E (0.05) −E (2.5))

(Method of Evaluating Reproducibility of Halftone Halftone) The halftone point (target halftone 50%) at an exposure amount giving a solid density of 3.5
%), Which was actually reproduced on the sample. 50%
The closer to, the better.

(Residual color) The unexposed sample was processed
Five samples were stacked and the sample containing no the compound of the present invention or the comparative compound was 5. The level where the residual color was extremely badly unworthy of evaluation was 1. The level which was not practically usable was 2. The one which was barely practical level. A visual relative evaluation was performed in a five-step evaluation of 3

The results obtained are shown in Table 9.

[0327]

[Table 9] As is clear from Table 9, the silver halide photographic light-sensitive material of the present invention has good halftone dot reproducibility.

Example 7 Using the emulsion described in Example 5, according to Example 5, silver halide photographic material samples 701 to 701 having the following five layers were prepared.
713 was created.

(Solid Disperse Dye Layer) Gelatin 7.0 g / m ² Saponin 80 mg / m ² Sodium polystyrene sulfonate (average molecular weight 500000) 15 mg / m ² Fungicide Z 0.5 mg / m ² Solid disperse dye; K7. 5 mg / m ²

(Silver Halide Emulsion Layer 1) Silver Halide Emulsion C-1 Amount of silver equivalent to 1.5 g / m ² Sensitizing dye; d-2 150 mg / Ag 1 mol Hydrazine compound; H-6 15 mg / m ² amine Compound: Na-21 35 mg / m ² Sodium-iso-amyl-n-decylsulfosuccinate 1.7 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 (average molecular weight 70,000) 10 mg / m ² Polymer latex; L2 (Example 3 type in JP-A-5-66512) Lx-3 composition (9)) 0.25 g / m ² colloidal silica (average particle size 0.05 μm) 150 mg / m ² The present compound or comparative compound shown in Table 10 in the form of addition shown in Table 10 Phthalated gelatin 1.2 g / m ^{2 The} coating solution pH was 4.8.

(Intermediate layer) Gelatin 0.8 g / m ² Sodium polystyrene sulfonate (average molecular weight 500000) 15 mg / m ² Fungicide Z 0.5 mg / m ²

(Silver Halide Emulsion Layer 2) Silver Halide Emulsion C- ² Equivalent amount of silver 0.3 g / m ² Gelatin 0.3 g / m ² Sensitizing dye; d-1 200 mg / Ag 1 mol Hydrazine compound; H -6 4 mg / m ² amine compound; Na-21 8 mg / m ² Compound a 100 mg / m ² 2-pyridinol 1 mg / m ² Polymer latex; L1 (average particle size 0.25 μm) 0.25 g / m ² hardener H1 5 mg / m ² sodium-iso-amyl-n-decylsulfosuccinate 0.7 mg / m ² sodium naphthalenesulfonate 8 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 of ascorbic acid ^{20mg / m 2 EDTA 25mg / m} 2 of polystyrene scan Amounts shown in Table 10 in addition form shown in the present invention compound or comparative compound in Table 10 is shown in the sodium acid 15 mg / m ² Table 10

(Emulsion protective layer) Gelatin 0.5 g / m ² sodium-iso-amyl-n-decylsulfosuccinate 12 mg / m ² matting agent; spherical polymethyl methacrylate having an average particle size of 3.5 μm 25 mg / m ² mat Agent; average particle size 8 μm amorphous silica 12.5 mg / m ² surfactant; S1 26.5 mg / m ² slip agent (silicone oil) 4 mg / m ² compound a 50 mg / m ² polymer latex; L3 (average particle size 0.15 μm) 0.25 g / m ² colloidal silica (average particle size 0.05 μm) 150 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Hardener; h2 30 mg / m ² polystyrene sulfonic acid Sodium 10 mg / m ² Fungicide Z 0.5 mg / m ²

The obtained sample was exposed and exposed in the same manner as in Example 5.
After processing, the sensitivity, γ, halftone dot reproducibility, middle dot reproducibility, and residual color were evaluated in the same manner as in Example 5.

[0335] The sensitivity was 100% of the sensitivity of the sample 708.
Relative sensitivity.

The results obtained are shown in Table 10.

[0337]

[Table 10]

Example 8 (Preparation of Silver Halide Emulsion D) The following solution A and the following solution B were mixed in the following solution C with a silver potential (EAg) of 120 mV.
At pH 3.0, 35 ° C., added in 7 minutes by double-mixing method,
AgCl 70% with average particle size 0.09 μm, AgBr30
% Nuclei.

Thereafter, the silver potential was adjusted to 100 mV with NaCl, the following solution D and the following solution E were added over 15 minutes, and AgCl 70 having an average particle size of 0.20 μm (coefficient of variation 15%) was added.
% And AgBr 30%.

Thereafter, the pH of the mixture was adjusted to pH 5 with a 1N aqueous solution of NaOH.
The sensitizing dye S-1 was added at 2 × 10 ^-4 mol per mol of silver, and the mixture was aged 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 the dispersion, 4 × 10 ⁻⁴ mol of chloramine T was added per 1 mol of silver, and the silver potential was 190 mV (40 mV).
C.) was prepared.

Solution A 16 g of silver nitrate 5.3 ml of nitric acid 5 ml 48 ml of ion-exchanged water

Solution B NaCl 3.8 g KBr 3.5 g ossein gelatin 1.7 g Deionized water 48 ml

Solution C NaCl 1.4 g Ossein gelatin 7 g Nitric acid 5% 6.5 ml K ₂ RhCl ₅ (H ₂ O) 0.06 mg Deionized water 700 ml

Solution D 154 g of silver nitrate 4.5 ml of 5% nitric acid 200 ml of ion-exchanged water

Solution E NaCl 37 g KBr 33 g Ossein gelatin 6 g K ₂ RhCl ₅ (H ₂ O) 0.04 mg Deionized water 200 ml

To the obtained emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 1.5 × 10 ⁻³ mol per mol of silver, and potassium bromide was added per mol of silver. 8.5 × 10 ^-4 mol were added and the pH was adjusted to 5.6, EA
g was adjusted to 123 mV.

Then, 2 × 10 ^-5 mol per mol of silver and 1.5 × 10 ^-5 mol of chloroauric acid per mol of silver were added as sulfur atoms with sulfur flakes dispersed in the form of fine particles as sulfur atoms.
For 80 minutes. Thereafter, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver, and 1-phenyl-5-mercaptotetrazole was added in an amount of 3 × 10 ⁻ per mol of silver. ⁴ mol and 1.5 × 10 ^-3 mol of potassium iodide were added per mol of silver. After cooling to 40 ° C., 2 × 10 ^-4 mol of sensitizing dye S-2 was added per mol of silver.

(Preparation of silver halide photographic material) On one surface of the support provided with an undercoat layer, from the support side, [solid disperse dye layer], [silver halide emulsion layer], [intermediate layer] [Emulsion protective layer] is formed by simultaneous multi-layer coating so as to be formed in this order, and after cooling and setting, on the opposite side of the support, from the support side, a “backing layer” having the following composition,
The “backing protective layer” is formed by simultaneous multi-layer coating so as to be formed in this order, cooled and set at −1 ° C., and simultaneously dried on both sides.
~ 812.

(Solid Disperse Dye Layer) Gelatin 0.7 g / m ² solid disperse dye; DF-1 15 mg / m ² water-soluble dye; f6 5 mg / m ² sodium-iso-amyl-n-decylsulfosuccinate 2 mg / m ² Compound of the present invention or comparative compound shown in Table 11 Amount shown in Table 11 in the form of addition shown in Table 11

(Silver halide emulsion layer) Silver halide emulsion D Silver amount 3 g / m ² Gelatin 1.5 g / m ² Hydrazine compound; H-6 1.5 mg / m ² Hydrazine compound; H-78 mg / m ² Polymer latex; L2 (Example 3 of Japanese Patent Application Laid-Open No. 5-66512, type Lx-3 composition (9)) 0.5 g / m ² 75% by weight of colloidal silica, 12.5% by weight of vinyl acetate, 12.5% by weight of vinyl pivalinate % Suspension polymer 1.0 g / m ² saponin 20 mg / m ² 2-mercapto-6-hydroxypurine 2 mg / m ² ascorbic acid 20 mg / m ² EDTA · 2Na 25 mg / m ² sodium polystyrene sulfonate (average molecular weight 50 10,000) The pH of the 15 mg / m ² coating solution was 5.2.

(Intermediate layer) Gelatin 0.42 g / m ² amine compound; Na-21 12.9 mg / m ² polymer latex; L2 (Japanese Unexamined Patent Publication No. 5-66512, Example 3, Type Lx-3 composition (9)) 0.3 g / m ² Sodium polystyrene sulfonate (average molecular weight 500,000) 10 mg / m ² Compound of the present invention shown in Table 11 or Comparative compound Amount shown in Table 11 in the form of addition shown in Table 11

(Protective Layer) Gelatin 0.48 g / m ² water-soluble dye; f7 50 mg / m ² sodium-iso-amyl-n-decylsulfosuccinate 12 mg / m ² compound; SU-1 0.6 mg / m ² Matting agent; average particle size 3 μm amorphous silica 22.5 mg / m ² Hydroquinone 50 mg / m ² Dimethyl siloxane (average molecular weight 100,000) dispersion (average particle size 0.2 μm) 12 mg / m ² Hardener: HA-1 140 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Fungicide; Z 0.5 mg / m ²

(Backing Layer) Gelatin 3.0 g / m ² sodium-iso-amyl-n-decylsulfosuccinate 5 mg / m ² compound; SU-3 50 mg / m ² colloidal silica 75% by weight, vinyl acetate 12. Suspension polymer of 5% by weight, vinyl pivalinate 12.5% by weight 0.6 g / m ² Sodium polystyrene sulfonate 10 mg / m ² dye; f4 120 mg / m ² dye; f2 15 mg / m ² dye; f5 37 mg / m ² 1-phenyl-5-mercaptotetrazole 3 mg / m ² Compound e 50 mg / m ² Hardener; HA-2 100 mg / m ²

(Backing protective layer) Gelatin 1.1 g / m ² matting agent; monodispersed polymethyl methacrylate having an average particle size of 3 μm 45 mg / m ² sodium-di (2-ethylhexyl) -sulfosuccinate 10 mg / m ²

With respect to the obtained sample, the sensitivity and γ were measured as described below, and the evaluation was made on the evaluation of enlargement, bright spot reproducibility, and residual color. Table 11 shows the obtained results.

(Measurement of Sensitivity and γ) The obtained sample was brought into close contact with a step wedge, exposed to tungsten light at 3200 ° K. for 3 seconds, and an automatic developing machine GR- 27 (manufactured by Konica Corporation) under the following conditions.

The blackening density of the treated sample was measured using PDA-65.
(Konica Digital Densitometer), the logarithm of the reciprocal of the exposure amount giving a blackening density of 1.0 was obtained, and the sensitivity was expressed as a relative sensitivity with the sample 812 being 100.

Also, the logarithm of the reciprocal of the exposure at which the density of 0.05 was obtained is E (0.05), and the log of the reciprocal of the exposure at which the density of 2.5 was obtained is E (2.5 ) Was determined by the following equation.

Γ = 2.45 / (E (0.05) −E (2.5))

(Evaluation of enlargement) SH1 manufactured by Konica Corporation
00E film with Adobe Select Set 500
Exposure at 0, small point (5% halftone dot), middle point (50% halftone dot), large point (95% dot) at 3600 dpi / 300 lpi
Using a sample with plain knitting of solid dots and a solid (100% halftone dots) as a manuscript, the obtained sample was enlarged to 120% by a fine zoom C-880F manufactured by Dainippon Screen Co., Ltd. Exposure is performed so that 95% of the step wedge of the original becomes 5%, and an automatic developing machine GR-2 is used using a developing solution and a fixing solution having the following compositions.
7 (manufactured by Konica Corporation) under the following conditions.

[0361] Of the processed sample exposed so that 95% halftone dot% of the original is reproduced to 5%, halftone% of the portion where the 5% portion of the original was exposed (the portion where 95% is to be reproduced) ) Was measured using X-Rite361T, and the elongation was evaluated.

(Reproducibility of Myo-go) The obtained sample was exposed as an original using Ugra chart as a document by Fine Zoom C880F manufactured by Dainippon Screen Co., Ltd., and an automatic developing machine GR-27 was prepared using a developing solution and a fixing solution having the following compositions. (Konica Corporation
Manufactured under the following conditions.

The light reproducibility was evaluated based on the black line width obtained by reproducing the 55 μm white fine lines when the exposure was performed so that the 55 μm black fine lines fall through the 55 μm line width.

(Residual color) The unexposed sample was processed
Five samples were stacked on top of each other, and the sample containing neither the compound of the present invention nor the comparative compound was 5, the level of the residual color was extremely bad and was not worthy of evaluation, the level was 2 which could not be realized, and the barely practical level. The relative evaluation by visual observation was performed in a five-step evaluation in which 3 was set.

[0365] (Developer Composition) used per liter of deionized water 224 ml DTPA · 5Na 1.0 g Potassium sulfite 12.54g sodium sulfite 42.58g KBr 4g H ₃ BO ₃ 8g of potassium carbonate 55g diethylene glycol 40 g 5-methylbenzotriazole 0 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 with pure water. When using, mix 600 ml of pure water to 1 L
To use. The pH of the working solution was 10.40.

(Fixing solution composition) 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 water salt per liter of working solution 18 g According to the above-mentioned recipe, it melt | dissolved and completed it with pure water to 400 ml. When using, mix 600 ml of pure water to 1 L
To use. The pH of the working solution was 4.83.

(Processing Conditions) (Step) (Temperature) (Time) Development 35 ° C. 30 seconds Fixing 35 ° C. 20 seconds Water 15 ° C. 20 seconds Squeeze / Drying 45 ° C. 30 seconds Total 100 seconds

[0368]

[Table 11]

Example 9 (Adjustment of silver halide photographic light-sensitive material) On one surface of a support provided with an undercoat layer, from the side of the support, [solid dispersion dye layer] and [silver halide emulsion layer 1] having the following compositions , [Silver halide emulsion layer 2], [intermediate layer] and [emulsion protective layer] are formed by simultaneous multi-layer coating so as to be formed in this order, and after cooling and setting, the support is provided on the opposite side of the support. From the body side, a “backing layer” and a “backing protective layer” having the following composition were formed by simultaneous multi-layer coating so as to be formed in this order, cooled and set at −1 ° C., and dried on both sides simultaneously. Photosensitive material samples 901 to 915 were obtained.

(Solid Disperse Dye Layer) Gelatin 0.7 g / m ² solid disperse dye; DF-1 15 mg / m ² water-soluble dye; f6 5 mg / m ² sodium-iso-amyl-n-decylsulfosuccinate 2 mg / m ²

(Silver halide emulsion layer 1) Silver halide emulsion D Silver amount 3 g / m ² Gelatin 1.5 g / m ² Hydrazine compound; H-6 1.5 mg / m ² Hydrazine compound; H-78 mg / m ² polymer latex; L2 (Example 3 type Lx-3 composition (9) in JP-A-5-66512) 0.5 g / m ² 75% by weight of colloidal silica, 12.5% by weight of vinyl acetate, 12.5% by weight of vinyl pivalinate Weight% suspension polymer 1.0 g / m ² saponin 20 mg / m ² 2-mercapto-6-hydroxypurine 2 mg / m ² ascorbic acid 20 mg / m ² EDTA · 2Na 25 mg / m ² sodium polystyrene sulfonate (average molecular weight 500,000) the amount the coating solution indicated pH for the present invention compounds are shown in 15 mg / m ² Table 12 or added form shown in Comparative compound Table 12 Table 12 It was 5.2.

(Silver halide emulsion layer 2) Silver halide emulsion D Silver amount 0.3 g / m ² Gelatin 0.2 g / m ² Hydrazine compound; H-6 0.2 mg / m ² Hydrazine compound; H-70 0.1 mg / m ² amine compound; Na-21 1.5 mg / m ² saponin 2 mg / m ^{2 The} compound of the present invention shown in Table 12 or the comparative compound The amount shown in Table 12 in the form of addition shown in Table 12 The coating solution pH was 5 .2.

(Intermediate layer) Gelatin 0.42 g / m ² amine compound; Na-21 12.9 mg / m ² polymer latex; L2 (Japanese Unexamined Patent Publication No. 5-66512, Example 3, type Lx-3 composition (9)) 0.3 g / m ² Sodium polystyrene sulfonate (average molecular weight 500,000) 10 mg / m ² Compound of the present invention or comparative compound shown in Table 12 Amount shown in Table 12 in the form of addition shown in Table 12

(Protective Layer) Gelatin 0.48 g / m ² water-soluble dye; f7 50 mg / m ² sodium-iso-amyl-n-decylsulfosuccinate 12 mg / m ² compound; SU-1 0.6 mg / m ² Matting agent; average particle size 3 μm amorphous silica 22.5 mg / m ² Hydroquinone 50 mg / m ² Dimethyl siloxane (average molecular weight 100,000) dispersion (average particle size 0.2 μm) 12 mg / m ² Hardener: HA-1 140 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² Fungicide Z 0.5 mg / m ²

(Backing Layer) Gelatin 3.0 g / m ² Sodium-iso-amyl-n-decylsulfosuccinate 5 mg / m ² compound; SU-3 50 mg / m ² colloidal silica 75 wt%, vinyl acetate 12. Suspension polymer of 5% by weight, vinyl pivalinate 12.5% by weight 0.6 g / m ² Sodium polystyrene sulfonate 10 mg / m ² dye; f4 120 mg / m ² dye; f2 15 mg / m ² dye; f5 37 mg / m ² 1-phenyl-5-mercaptotetrazole 3 mg / m ² Compound e 50 mg / m ² Hardener; HA-2 100 mg / m ²

(Backing protective layer) Gelatin 1.1 g / m ² matting agent; monodispersed polymethyl methacrylate having an average particle size of 3 μm 45 mg / m ² sodium-di (2-ethylhexyl) -sulfosuccinate 10 mg / m ²

The obtained sample was measured for sensitivity and γ in the same manner as in Example 8, and evaluated for grain enlargement, light spot reproducibility and residual color. The sensitivity was represented by a relative sensitivity where Sample 915 was set to 100. Table 12 shows the obtained results.

[0378]

[Table 12]

[0379]

According to the present invention, a silver halide photographic material for photoengraving has a relatively low pH (pH 7.5).
Halogenated, which is an image forming material that provides a stable and ultra-high contrast image even in processing with a developing solution, has good reproducibility of Mincho / Gothic characters, and has a wide halftone reproduction range. A silver photographic light-sensitive material could be provided.

Also, a silver halide color photographic light-sensitive material having good graininess and sharpness could be provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 381/14 C07C 381/14 C07D 213/76 C07D 213/76 213/78 213/78 233/84 233/84 235/28 235 / 28 B 249/12 510 249/12 510 271/10 271/10 277/64 277/64 285/135 333/20 285/125 333/32 333/20 401/12 249 333/32 405/12 213 401 / 12 249 409/04 249 405/12 213 409/12 249 409/04 249 409/14 213 409/12 249 473/00 409/14 213 487/04 146 473/00 G03C 1/06 501 487/04 146 1/295 G03C 1/06 501 1/43 1/295 5/29 501 1/43 C07D 285/12 E 5/29 501 D (72) Inventor Hirohide Ito 1 Sakuramachi, Hino-shi, Tokyo Konica Corporation (72) Inventor Toshiyuki Takabayashi, Konica Corporation, 1 Sakuracho, Hino-shi, Tokyo

Claims (20)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer, characterized in that it contains at least one compound which is oxidized by an oxidized form of a developing agent and changes into a development inhibitor. Silver halide photographic material. 2. The silver halide according to claim 1, wherein the compound which is oxidized by an oxidized form of the developing agent and changes into a development inhibitor is a compound represented by the following general formula (1). Photosensitive material. Embedded image [In the formula, R, R 'and R "represent a hydrogen atom or a monovalent substituent.] 3. A compound represented by the general formula (1):
The monovalent substituent represented by R 'is a monovalent aromatic ring residue or a heterocyclic residue, and at least one of them has an electron donating group. 3. The silver halide photograph according to claim 2, wherein the monovalent substituent is a compound represented by the general formula (1), which is a monovalent aromatic ring residue or a heterocyclic residue. 3. A photosensitive material, wherein the compound represented by the general formula (1) is R,
The monovalent substituent represented by R 'is a monovalent aromatic ring residue or a heterocyclic residue, and at least one of them has an electron donating group. 3. The silver halide photograph according to claim 2, wherein the monovalent substituent is a compound represented by the general formula (1), which is a monovalent aromatic ring residue or a heterocyclic residue. Photosensitive material. 4. A compound represented by the general formula (1):
4. The compound according to claim 2, wherein at least one of the monovalent substituents represented by R 'and R "is a compound represented by the general formula (1) having an adsorptive group to silver halide. The silver halide photographic light-sensitive material as described above. 5. The silver halide photographic light-sensitive material according to claim 4, wherein the adsorptive group is an adsorptive group having a thioether structure. 6. A compound represented by the general formula (1):
At least one of the monovalent substituents represented by R ′ and R ″ is a water-soluble group or a compound represented by the general formula (1) having a water-soluble group as a substituent. Item 6. The silver halide photographic material according to any one of Items 2 to 5. 7. The silver halide photograph according to claim 2, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2). Photosensitive material. Embedded image [Wherein, Y, Y ′ and Y ″ represent monovalent substituents.
m and n represent the integer of 0-5. ] 8. The compound represented by the general formula (2), wherein Y is
8. The compound according to claim 7, wherein at least one of the monovalent substituents represented by Y 'and Y "is a compound represented by formula (2) having an adsorptive group to silver halide. Silver halide photographic material. 9. The silver halide photographic material according to claim 8, wherein the adsorptive group is an adsorptive group having a thioether structure. 10. The compound represented by the general formula (2) is represented by Y,
A compound represented by general formula (2) in which at least one of the monovalent substituents represented by Y ′ and Y ″ is a water-soluble group or a substituent having a water-soluble group as a substituent. The silver halide photographic light-sensitive material according to any one of claims 7 to 9, wherein 11. A method according to claim 1, wherein a compound which is oxidized by an oxidized form of a developing agent and changes into a development inhibitor is added to a photographic component layer other than the emulsion layer. The silver halide photographic light-sensitive material as described above. 12. The silver halide photographic material according to claim 1, further comprising a nucleating agent. 13. The silver halide photographic material according to claim 12, wherein the nucleating agent is a hydrazine derivative. 14. The silver halide photographic material according to claim 1, further comprising a nucleation accelerator. 15. The silver halide photographic light-sensitive material according to claim 14, wherein the nucleation accelerator is an amine compound. (16) After the silver halide photographic light-sensitive material according to any one of (1) to (15) is imagewise exposed, the pH is 7.5.
A method for processing a silver halide photographic light-sensitive material, wherein the development processing is carried out with a developing solution having a content of less than 10.5. 17. A formazan compound represented by the following general formula (3). 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. ] 18. A compound represented by the general formula (3):
At least one of the monovalent substituents represented by R ′ and R ″ is a compound represented by the general formula (3), which is a water-soluble group or a substituent having a water-soluble group as a substituent. A formazan compound according to claim 17, characterized in that: 19. A formazan compound represented by the following general formula (4). 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.] 20. A compound represented by the general formula (4):
At least one of the monovalent substituents represented by Y ′ and Y ″ is a compound represented by the general formula (4), which is a water-soluble group or a substituent having a water-soluble group as a substituent. A formazan compound according to claim 19, characterized in that: