JPH11271910A - Silver halide photographic sensitive material and its manufacture and image forming method by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the photographic sensitive material capable of forming an image high in contrast and stability by exposure in an extremely short time by using >=2 kinds of silver halide emulsions different from each other in an adsorption amount of a hydrazine derivative. SOLUTION: The silver halide emulsions to be used are >=2 kinds of emulsions different from each other in an adsorption amount of the hydrazine derivative. The adsorption amount of the hydrazine derivative can be changed by adding the hydrazine derivative until mixing each emulsion, or adding it after mixing the emulsions and after finishing chemical ripening in order to prevent uniformization of the hydrazine derivative and it is especially preferred to add it after finishing the chemical ripening until adding a sensitizing dye. It can be attained also by adding the hydrazine derivative stronger in adsorbing power to the emulsion more in an amount of adsorbing the hydrazine derivative. It is preferred that the sensitivity of the emulsion is lower in the absence of action of the hydrazine derivative, in the case that the emulsion more adsorbs the hydrazine derivative.

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 (hereinafter, simply referred to as "light-sensitive material" and "light-sensitive material") and an image forming method and a manufacturing method of the silver halide photographic light-sensitive material. The present invention relates to a silver halide photographic light-sensitive material for printing plate making, an image forming method and a manufacturing method of a silver halide photographic light-sensitive material for printing plate making.

[0002]

2. Description of the Related Art Conventionally, in the printing and plate making process, a form of direct output from an image setter after editing on a system has become widespread in recent years with the progress of digitization. As a photographic light-sensitive material desired for such a working mode, a light-sensitive material having high contrast and high stability by an extremely short exposure of less than 10 ^-6 seconds by a laser beam is desired. Conventionally, output from an image setter has not required much processing speed because it took time to develop image data by RIP, but in recent years the processing speed of photographic light-sensitive materials has been reduced due to a significant increase in calculation speed. Is becoming rate-limiting in increasing productivity. Therefore, it is strongly desired to increase the processing speed. However, it is a major problem that a photosensitive material having high contrast and high stability cannot be obtained by an extremely short exposure of less than 10 ^-6 seconds by a laser beam. .

On the other hand, a method for using two or more kinds of silver halide emulsions in a silver halide photographic light-sensitive material containing a hydrazine derivative is disclosed in JP-A-61-223732.
Nos. 63-6437 and JP-A-7-301878, etc., but nothing was focused on the adsorption amount of the hydrazine derivative.

[0004]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a light-sensitive material having high contrast and high stability in an extremely short exposure time, a method for producing the light-sensitive material, and a method for manufacturing the same. An object of the present invention is to provide an image forming method with high productivity.

[0005]

The above object of the present invention is attained by the following constitutions.

(1) At least one side on one side of the support
A silver halide photographic light-sensitive material comprising two or more silver halide emulsions having different adsorption amounts of hydrazine derivatives in a silver halide photographic light-sensitive material having a silver halide emulsion layer.

(2) The silver halide photographic material as described in (1) above, wherein the silver halide emulsion having a large amount of hydrazine derivative adsorbed has low sensitivity.

(3) The average particle size of silver halide grains in a silver halide emulsion having a large amount of adsorption of a hydrazine derivative is smaller than the average particle size of silver halide particles in a silver halide emulsion having a small amount of adsorption of a hydrazine derivative. The silver halide photographic material as described in the above item (1) or (2),

(4) A silver halide emulsion having a larger amount of hydrazine derivative adsorbed than a silver halide emulsion having a smaller amount of hydrazine derivative adsorbed on silver halide grains by a transition metal belonging to Groups 6 to 10 of the periodic table. The silver halide photographic light-sensitive material according to the above (1), (2) or (3), wherein the number is larger.

(5) When the transition metal of Groups 6 to 10 of the periodic table is R
h, Ru, Re, and Os. The silver halide photographic material as described in (4) above, wherein

(6) The above (1), (2), (3),
(4) An image forming method wherein the image is obtained by imagewise exposing the silver halide photographic material described in (5), developing the image with a developing time of less than 20 seconds, fixing, washing and drying. Method.

(7) The image forming method according to the above (6), wherein the exposure time of the silver halide photographic material is less than 10 ^-6 seconds.

(8) At least one side on one side of the support
A method for producing a silver halide photographic material, comprising using two or more silver halide emulsions having different adsorption amounts of a hydrazine derivative in a silver halide photographic material having a silver halide emulsion layer. A method for producing a silver halide photographic material, comprising adding a hydrazine derivative at the end of chemical ripening.

Hereinafter, the present invention will be described in detail.

The silver halide emulsion of the present invention is to use two or more kinds of silver halide emulsions having different adsorption amounts of the hydrazine derivative used as a high contrast agent. The method of changing the amount of the hydrazine derivative adsorbed to the silver halide emulsion is achieved by adding the hydrazine derivative until the respective emulsions are mixed. Further, in order to prevent homogenization of the hydrazine derivative after the emulsion is mixed, a method of adding the hydrazine derivative at the time of completion of chemical ripening is used. Particularly preferably, it is added after completion of chemical ripening and before addition of the sensitizing dye. A method used before the completion of chemical ripening is also preferably used.

It is also achieved by using a hydrazine derivative having a high adsorptive power in an emulsion having a higher adsorption amount of the hydrazine derivative.

The amount of the hydrazine derivative adsorbed on the silver halide emulsion is not less than 1 × 10 ^-6 mol and not more than 1 × 10 ⁶ mol per mol of Ag.
^-2 mol or less, particularly preferably 1 × 10 ⁻⁵ mol or more and 1 × 10 ⁻³ mol or less.

Emulsions having a high adsorption amount of the hydrazine derivative preferably have an adsorption amount per mol of silver of 1.3 to 100 times, more preferably 1. The adsorption amount is 5 times or more and 20 times or less, particularly preferably 2 times or more and 10 times or less.

In the present invention, it is preferable that the emulsion having a large amount of adsorption of the hydrazine derivative has a low emulsion sensitivity when viewed without the action of the hydrazine derivative. As a method for changing the sensitivity of the silver halide emulsion, various methods such as adjustment of the degree of chemical ripening, adjustment of color sensitization, particle diameter of the silver halide emulsion, and a method using a doped metal are used.
It is also preferable to use a combination of several methods to provide a sensitivity difference.

The difference in sensitivity between silver halide emulsions is at least 0.1 log.
It is preferable to attach at least 05, more preferably 0.1
It is 5 or more and 2.0 or less, particularly preferably 0.2 or more and 1.5 or less.

The hydrazine derivative used in the silver halide photographic light-sensitive material of the present invention is preferably a compound represented by the following formula [H].

[0022]

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In the general formula [H], A represents an aryl group,
Or a heterocyclic ring containing at least one sulfur atom or oxygen atom, and G represents a — (CO) _n — group, a sulfonyl group, a sulfoxy group, a —P (＝ O) R ₂ — group, or an iminomethylene group. , N represents an integer of 1 or 2, A ₁ and A _{2 each} represent a hydrogen atom or one of which is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted acyl group; A hydrogen atom represents a substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino group, carbamoyl group, or oxycarbonyl group. R ₂ is a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group,
Represents an alkenyloxy group, an alkynyloxy group, an aryloxy group, an amino group, or the like.

Among the compounds represented by the general formula [H], more preferred are the compounds represented by the following general formula [Ha].

[0025]

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In the general formula [Ha], R ¹ represents an aliphatic group (for example, octyl group, decyl group), an aromatic group (for example, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or a heterocyclic group (for example, pyridyl group) , A thienyl group, a furyl group), and those groups further preferably substituted with a suitable substituent are preferably used. Further, R ¹ preferably contains at least one ballast group or silver halide adsorption group.

As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, an alkyl group having a carbon number of 8 or more which is relatively inert to photographic properties, for example, an alkyl group Alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

As the silver halide adsorbing group, thiourea,
Examples thereof include a thiourethane group, a mercapto group, a thioether group, a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

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

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

In the general formula [Ha], G ¹ represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G ¹ is preferably a carbonyl group.

In the general formula [Ha], R ² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group,
Represents a carbamoyl group or an oxycarbonyl group. Most preferred R ² includes a —COOR ³ group and —CON (R ⁴ )
(R ⁵ ) group and fluorine-substituted alkyl group (R ³ represents an alkynyl group or a saturated heterocyclic group, and R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. , R ⁵ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group).

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

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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Specific examples of other preferable hydrazine derivatives include (1) to (252) described in US Pat. No. 5,229,248, columns 4 to 60.

The above hydrazine derivative can be synthesized by a known method. For example, US Pat.
No. 248, column 59 to column 80, can be synthesized by the method as described.

In the present invention, it is preferable to use a nucleation accelerator in order to effectively promote the contrast enhancement by the hydrazine derivative.

As a preferred nucleation accelerator, a compound represented by the following formula (Na) or (Nb) is preferably used.

[0043]

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In the general formula (Na), R ₃₁ , R ₃₂ , R
₃₃ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group,
Represents a substituted aryl group, and R ₃₁ , R ₃₂ and R ₃₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is particularly preferable. Preferred adsorbing groups include a heterocyclic ring, a mercapto group, a thioether group,
Examples include a selenoether group, a thione group, and a thiourea group. Particularly preferred as the general formula (Na) are compounds having at least one thioether group as a halogen adsorbing group in the molecule.

The following are specific examples of these nucleation accelerators (Na).

[0046]

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[0047]

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[0048]

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[0049]

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In the general formula (Nb), Ar represents a substituted or unsubstituted aromatic or heterocyclic group. R ₃₄ is a hydrogen atom, an alkyl group, an alkynyl group, an aryl group,
Ar and R ₃₄ may be linked by a linking group to form a ring.
These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Preferred examples of the silver halide adsorption group include groups having the same meaning as the silver halide adsorption group of the compound represented by the formula [H].

Specific compounds of the general formula (Nb) include the following.

[0052]

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[0053]

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Specific examples of other preferred nucleation accelerators include:
The example described in JP-A-6-258751 (2-
Compounds 1) to (2-20) and (3-1) to (3-6) described in JP-A-6-258755, JP-A-7-27095
Onium salt compound described in No. 7, JP-A-7-104420
Compound of general formula I of JP-A-2-103536
From page 19, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, and thiosulfonic acid compounds described in JP-A-1-237538.

The average grain size of the silver halide emulsion used in the present invention is preferably 0.6 μm or less, more preferably 0.05 to 0.5 μm. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details on how to determine the average particle size, see Mees,
James: The Theory of the Photographic Process (CE Mees & TH James)
Written by The theory of the photo
graphic process), 3rd edition, 36-4
See page 3 (1966, Macmillan).

In the present invention, the emulsion having a large amount of adsorption of the hydrazine derivative preferably has a smaller particle size than the emulsion having a small amount of adsorption. The difference in particle size at that time is 10% or more 5
00% or less, more preferably 1% or less.
5% or more and 200% or less, particularly preferably 20% or more and 10% or less
0% or less.

As for the composition of the silver halide emulsion, it is preferable to use a silver halide emulsion having a silver chloride content of 60 mol% or more, and specifically, silver chloride, a salt smell containing 60 mol% or more of silver chloride. It is preferable to use a silver halide emulsion having a composition of silver halide and silver chloroiodobromide containing 60 mol% or more of silver chloride.

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 particle size distribution is preferably narrow, and in particular, 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size.
So-called monodisperse emulsions are preferred.

Of the above tabular grains, tabular grains having a (100) plane having 90 mol% or more of silver chloride as a main plane can be used, and these are disclosed in US Pat. No. 5,264,3.
No. 37, 5,314,798, 5,320,95
No. 8, etc., and target tabular grains can be easily obtained.

In the present invention, the method of reacting the soluble silver salt with the soluble halogen salt may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof. 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, that is, a so-called controlled double jet method can be used. To obtain a silver halide emulsion having a nearly uniform grain size.

In the present invention, the silver halide emulsion preferably contains one compound selected from transition metals of Groups 6 to 10 of the periodic table.

The transition metal complex preferably used in the present invention is a six-coordinate complex represented by the following general formula [1].

General formula [1] [ML ₆ ] ^{m In} general formula [1], M is a transition metal selected from elements of Groups 6 to 10 of the periodic table, L is a bridging ligand, m is 0,-
Represents 1, -2 or -3. Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate,
Examples include selenocyanate, tellurocyanate, azide and aquo ligands, nitrosyl, thionitrosyl and the like. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

A preferred example of M is rhodium (R
h), ruthenium (Ru), rhenium (Re), osmium (Os) and iridium (Ir).

Specific examples of the transition metal coordination complex (hereinafter, also referred to as metal complex) are shown below.

[0066] 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [CrCl _6] ^{4 -} 7: [Ru (NO) Cl _5] ^2- 8: [RuBr ₄ (H ₂ O) _2] ^- 9: _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 10: [RhCl ₅ (H ₂ O)] ^2-11 : [Re (NO) Cl ₅ ] ^2-12 : [Re (NO) (CN) ₅ ] ^2-13 : [Re (NO) Cl (CN) ₄ ] ^2-14 : [Rh (NO) ₂ Cl _4] ^- 15: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 16: [Ru (NO) (CN) _5] ^2- 17: [Fe (CN) _6] ^3- 18 : [Rh (NS) Cl _5] ^2- 19: [Os (NO) Cl _5] ^2- 20: [Cr (NO) Cl _5] ^2- 21: [Re (NO) Cl _5] ^- 22: [Os (NS) Cl ₄ (TeCN)] ^2- 23: [Ru (NS) Cl _5] ^2- 24: _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 25: [Os (NS) Cl (SCN) 4 ] ^2- 26: [Ir (NO ) Cl ₅ ] ^2- metal complex can be added to silver halide during the preparation of silver halide grains. The timing of addition may be such that it is uniformly distributed throughout the silver halide grains, or it may be such that it is present in the inner shell of the silver halide grains. Particularly preferred transition metals used in the present invention are Rh, Ru, Re, and Os.

Although there is no particular limitation, the timing of addition is preferably at the time of particle formation. The addition amount is usually 10 ^-8 to 10 ^-3 mol, preferably 10 ^-10 mol, per mol of silver halide.
^-8 to 10 ^-6 mol. In particular, it is preferable that these transition metals belonging to groups 6 to 10 are more doped in a silver halide emulsion having a large amount of adsorption of a hydrazine derivative. The preferred doping ratio is 1.0 times or more and 100 times or less, and more preferably 1.2 times or more and 10 times or less.

The silver halide emulsion is preferably chemically sensitized. Known methods of chemical sensitization include sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization, and any of these methods may be used alone or in combination. As the sulfur sensitizer, known sulfur sensitizers can be used. Preferred sulfur sensitizers include, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, Rhodanins, polysulfide compounds and the like can be used. As the selenium sensitizer, a known selenium sensitizer can be used.

Combinations using these chemical sensitizers include, for example, a combination of a sulfur sensitizer and a noble metal sensitizer,
Examples include a combination of a selenium sensitizer and a noble metal sensitizer, and a combination of a reduction sensitizer and a noble metal sensitizer.

These chemical sensitizers can be added at any time during the preparation of the silver halide emulsion, but preferably at the time of chemical sensitization. The addition amount of these chemical sensitizers is preferably in the range of 10 ^-9 mol to 10 ^-3 mol per mol of silver halide.

The silver halide photographic light-sensitive material of the present invention preferably contains a developing agent. A preferable addition amount is 0.1 g / m ² or more and 5 g / m ² or less, and particularly preferably 0.2 g / m ² or more and 1.5 g / m ² or less. As the developing agent contained in the light-sensitive material, an appropriate one can be selected from conventionally known ones. The developing agent referred to here includes a developing agent precursor that releases the developing agent during development.

Examples of the developing agents which can be used in the present invention include, for example, US Pat. Nos. 3,351,286, 3,761,270, 3,764,328 and 3,342,599. No. 3,719,492, Research Disclosure No. 12146, No. 15108
No. 15,127, and JP-A-56-27132,
Nos. 53-135628 and 57-79035, p-phenylenediamine-based and p-aminophenol-based developing agents, phosphate amidophenol-based developing agents, sulfonamidoaniline-based developing agents, and hydrazone-based developing agents, Phenols, sulfonamide phenols,
There are polyhydroxybenzenes, naphthols, hydroxybisnaphthyls, methylenebisphenols, ascorbic acids, 1-aryl-3-pyrazolidones, hydrazones, and precursors of the above various developing agents.

In the present invention, the developing agent is preferably incorporated in a light-sensitive material (hereinafter also referred to as a light-sensitive material). Therefore, the number of carbon atoms of the developing agent is preferably 20 or less in view of the content and the efficiency of developable silver. And particularly preferably 15 or less carbon atoms.

Two or more developing agents may be used in combination, and 1-aryl-3-pyrazolidone or a derivative thereof and a hydroquinone derivative are particularly preferred.

These developing agents can be contained in the silver halide emulsion layer and other hydrophilic colloid layers. Preferably, the same side of the support as the silver halide emulsion layer is used, and more preferably, a hydrophilic colloid layer other than the silver halide emulsion layer is used. Particularly preferred is any layer between the support and the silver halide emulsion layer.

It is preferable that the developing agent used in the present invention is contained in a solid dispersion state from the viewpoint of the storage stability of the light-sensitive material. As a method of dispersion, an aqueous solution containing a developing agent substantially free of an organic solvent such as ethyl acetate, methanol, methyl ethyl ketone and the like and a high boiling point organic solvent and optionally containing one or more stabilizers or pulverizers may be used. Or a method of removing the organic solvent under reduced pressure after mixing with water, or repeatedly subjecting the solid of the developing agent to a hard inorganic grinding medium in an aqueous solution which may contain one or more stabilizers or grinding agents Prepared. Hard inorganic grinding media include sand, silica spheres, stainless steel, silicon carbide, glass, zirconium, zirconium oxide,
Use beads such as alumina and titanium. These bead sizes range from 0.25 to 3.0 mm. Ball mill, media mill, attritor mill, jet mill,
A method of reducing the particle size using a vibration mill or the like is also often used.

The average particle size of the dispersion obtained as described above can be in the range conventionally obtained by this method, and is generally about 0.05 to 1.5 μm, preferably 0 to 1.5 μm. 0.1 to 1.0 μm.

In the dispersion used in the present invention, a stabilizer or a dispersion aid is used. As the stabilizer or the dispersing aid, a surfactant or a hydrophilic colloid is preferable.

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

It is advantageous to use gelatin as a binder or protective colloid of the photographic emulsion according to the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers such as polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole Can be.

As the gelatin, in addition to lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

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

In the photographic emulsion and the non-photosensitive hydrophilic colloid layer of the present invention, an inorganic or organic hardener is added as a crosslinking agent for a hydrophilic colloid such as gelatin. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compound (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) ), Mucohalogenic acids (mucochloric acid, phenoxymucochloric acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, carboxyl group-activated hardener, etc., alone or in combination Can be used. These hardeners are described in Research Disclosure, Vol. 176, No. 17643 (1.
(December 978), page 26, paragraphs A to C.

Various other additives are used in the light-sensitive material of the present invention. For example, desensitizers, plasticizers, slip agents,
Development accelerators, oils and the like.

The support used in the present invention may be either permeable or non-permeable, but in order to achieve the object of the present invention, a permeable plastic support is preferred. As the plastic support, a support composed of a polyethylene compound (eg, polyethylene terephthalate, polyethylene naphthalate, etc.), a triacetate compound (eg, triacetate cellulose, etc.), a polystyrene compound (eg, syndiotactic polystyrene) or the like is used.

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

In the present invention, the following compounds are preferably contained in the constituent layers of the silver halide photographic light-sensitive material.

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

[0089]

[Table 1]

When the photosensitive material is imagewise exposed, an exposure time of less than 10 ^-6 seconds, which is a region where the high illuminance failure is large, is preferable in that the effect of the present invention is greater. More preferably, 10 ^-7
Preferably, the exposure time is less than seconds. Such an exposure method can be achieved by using various laser light sources. Preferred examples of the light source include a He-Ne laser, an Ar laser, a He-Cd laser, an infrared semiconductor laser, a red semiconductor laser, and an LED.

The black-and-white silver halide photographic material according to the present invention is subjected to photographic processing after exposure by an automatic processor having at least four processes of development, fixing, washing (or stabilizing bath) and drying.

As the developer used in the present invention, known developing agents can be used. Specifically, dihydroxybenzenes (eg, hydroquinone, hydroquinone monosulfonate, etc.), 3-pyrazolidones (eg, 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.), ascorbic acids (ascorbic acid, sodium ascorbate, erythorbic acid, etc.) and metal complexes (EDTA iron salt, DTPA iron) Salt, DTPA nickel salt, etc.) can be used alone or in combination. Among them,
It is preferable to use a developer containing ascorbic acid and its derivatives. Ascorbic acid and its derivatives
Known developing agents are described, for example, in US Pat.
88,548, 2,688,549, 3,022,
No. 168, 3,512,981, 4,975,354
No. 5,326,816 and the like can be used.

In the present invention, a developing agent of ascorbic acid or a derivative thereof and a 3-pyrazolidone (for example, 1
-Phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl -5-methyl-3
-Pyrazolidone, etc.) and aminophenols (for example, o-
Aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol and the like, and dihydroxybenzenes (for example, hydroquinone, hydroquinone monosulfonate, hydroquinone monosulfonic acid) It is more preferable to use a developing agent such as sodium salt or potassium 2,5-hydroquinonedisulfonate in combination. When used in combination, the developing agents of 3-pyrazolidones, aminophenols and dihydroxybenzenes are preferably used in an amount of usually 0.01 to less than 0.2 mol per liter of developer. Especially,
Combinations of ascorbic acid and its derivatives with 3-pyrazolidones and combinations of ascorbic acid and its derivatives with 3-pyrazolidones and dihydroxybenzenes are preferably used.

In the present invention, the developer contains an alkaline agent (eg, sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (eg, carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine). And the like are preferably added. The pH buffer is preferably a carbonate, and the amount of the carbonate added is preferably 0.5 mol or more and 2.5 mol or less per liter, more preferably 0.75 mol or more and 1.5 mol or less.
Molar range. If necessary, dissolution aids (eg, polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers (eg, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, Antifoaming agents, antifoggants (eg, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole,
Benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (eg, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, biodegradable chelating agents, etc.), development accelerators (eg, U.S. Pat. No. 2,304,025, Japanese Patent Publication No. 47
45541), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent.

The pH of the developing solution is controlled by the alkaline agent.
It is preferably adjusted to 5 or more and less than 10.5. More preferably, the pH is 8.5 or more and 10.4 or less.

As the fixing solution, those having a commonly used composition can be used. Fixers generally have a pH of 3
８8. As a fixing agent, sodium thiosulfate, potassium thiosulfate, thiosulfates such as ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate,
In addition to thiocyanates such as ammonium thiocyanate, organic sulfur compounds capable of forming a soluble stable silver complex salt and known as a fixing agent can be used.

The fixing solution contains a water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum, an aldehyde compound (for example, glutaraldehyde or a sulfurous acid adduct of glutaraldehyde).
Etc. can be added.

The fixing solution may contain, if desired, a preservative (eg, sulfite or bisulfite), a pH buffer (eg, acetic acid or citric acid), a pH adjuster (eg, sulfuric acid), a chelating agent having a water softening ability. A compound such as an agent can be included.

The fixing solution contains salts such as acetic acid, citric acid, tartaric acid, malic acid and succinic acid, and optical isomers thereof. As the salts of acetic acid, citric acid, tartaric acid, malic acid, succinic acid and the like, these lithium salts, potassium salts,
Lithium hydrogen tartaric acid, potassium hydrogen, sodium hydrogen, ammonium hydrogen, ammonium potassium tartaric acid, sodium potassium tartaric acid, and the like such as sodium salt and ammonium salt may be used.

As the developing solution and / or the fixing solution, a solution obtained by dissolving a solid processing agent such as a tablet or a granule in a solvent such as water can be used.

After the fixing treatment, it is washed and / or treated in a stabilizing bath. As the stabilizing bath, the pH of the film surface is adjusted for the purpose of stabilizing the image (the film surface pH after the treatment is adjusted to 3 to 8).
Inorganic and organic acids and salts thereof, or alkali agents and salts thereof (eg, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid) Acids, dicarboxylic acids,
Polycarboxylic acid, citric acid, oxalic acid, malic acid, acetic acid, etc. used in combination, aldehydes (eg, formalin, glyoxal, glutaraldehyde, etc.), chelating agents (eg, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetic acid salt) , Polyphosphates, etc.), anti-binders (for example, phenol, 4-chlorophenol, cresol, o-phenylphenol, chlorophen, dichlorophen, formaldehyde, p-hydroxybenzoate, 2- (4-thiazoline) -benzo) Imidazole, benzoisothiazolin-3-one, dodecyl-benzyl-methylammonium-chloride, N- (fluorodichloromethylthio) phthalimide, 2,4,4'-
Trichloro-2'-hydroxydiphenyl ether, etc.), color tone adjuster and / or residual color improver (for example, a nitrogen-containing heterocyclic compound having a mercapto group as a substituent;
Specifically, sodium 2-mercapto-5-sulfonate-benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole,
Mercapto-5-propyl-1,3,4-triazole, 2-mercaptohypoxanthine, etc.).
Among them, it is preferable that the stabilizing bath contains an anti-binder. These may be replenished in liquid or solid form.

In view of the demand for reducing the amount of waste liquid, the present invention is processed while replenishing a fixed amount of fixing in proportion to the area of the photosensitive material. The fixing replenishment amount is usually 300 m per 1 m ²
1 or less. Preferably 30 to 1 m ² each
250 ml.

Due to the demand for reduction of the amount of waste liquid, the replenishment amount of development is 1
preferably m is ² per 250ml or less, more preferably 30~200ml per 1 m ^2, respectively. The fixing replenishing amount and the developing replenishing amount referred to here indicate the replenishing amounts. Specifically, it is the replenishing amount of each of the developing mother liquor and the fixing mother liquor when replenishing the same liquor, and the respective concentrated liquor when the developing concentrated liquor and the fixing concentrated liquor are replenished with a solution diluted with water. And the total amount of water
This is the total amount of the solid processing agent and the solid fixing agent and water when the solid developing agent and the solid fixing agent are replenished with a solution prepared by dissolving in water. This is the total volume of each solid processing agent volume and water volume when replenished separately. When replenished with a solid processing agent, it is preferable to express the total amount of the volume of the solid processing agent directly charged into the processing tank of the automatic developing machine and the volume of the replenishing water added separately. The developing replenisher and the fixing replenisher may be the same as the developing mother liquor and the fixing mother liquor in the tank of the automatic developing machine, or different liquids or solid processing agents, respectively.

The temperature of the developing, fixing, washing and / or stabilizing bath is preferably in the range of 10 to 45 ° C., and each may be separately adjusted.

In the present invention, the total processing time (Dry to dry) from the insertion of the leading end of the film into the automatic developing machine to the emergence from the drying zone when processing using the automatic developing machine is 60 due to the demand for shortening the developing time. There is a high demand for processing in less than 10 seconds or more. (The term "total processing time" herein includes the total processing time required for processing a black-and-white photosensitive material, and specifically, for example, development, fixing, bleaching, washing, stabilizing processing, drying, etc., necessary for processing. However, it is a time including all of the time of the step (i.e., a dry-to-dry time.) However, if the addition amount of the hydrazine derivative is increased in order to achieve a high contrast in such a short processing time, black spots and fog may be reduced. There is a problem, and when the present invention is applied to such a processing process, the effect is large. From such a viewpoint, it is preferable to use in a processing process in which the development time is less than 20 seconds, and particularly preferably, the development time is less than 15 seconds.
Further, the total processing time (Dry to dry) is 15 to 50.
Preferably, it is seconds.

In order to remarkably exert the effects of the present invention, a heat conductor (for example, 60 to 60 ° C.) having a temperature of 60 ° C. or higher is required for an automatic developing machine.
130 ° C heat roller, etc.) or 150 ° C or higher radiant object (for example, tungsten, carbon, nichrome, a mixture of zirconium oxide, yttrium oxide, thorium oxide, silicon carbide, etc.) Those that transmit energy to a radiator such as copper, stainless steel, nickel, and various ceramics to generate heat or emit infrared rays) and have a drying zone are preferably used.

Examples of the heat transfer material of 60 ° C. or higher include:
A heat roller is mentioned as an example. The heat roller preferably has an aluminum hollow roller whose outer peripheral portion is covered with silicon rubber, polyurethane, or Teflon. Both ends of the heat roller are preferably disposed inside the vicinity of the transport port of the drying unit by bearings made of a heat-resistant resin (for example, Lulon), and are rotatably supported on the side wall.

A gear is fixed to one end of the heat roller, and is preferably rotated in the transport direction by a driving unit and a driving transmission unit. A halogen heater is inserted in the roller of the heat roller, and the halogen heater is preferably connected to a temperature controller provided in the automatic developing machine.

The temperature controller is connected to a thermistor arranged in contact with the outer peripheral surface of the heat roller. The temperature controller detects the temperature from the thermistor normally at 60 to 150 ° C., preferably at 70 to 130 ° C. As described above, it is preferable that the halogen heater be turned on and off.

The following examples are given as radiating objects emitting radiation temperature of 150 ° C. or higher. Tungsten, carbon,
Tantalum, nichrome, a mixture of zirconium oxide, yttrium oxide, and thorium oxide, silicon carbide, molybdenum disilicide, and lanthanum chromate are directly heated and radiated to control the radiation temperature, or heat energy is radiated from a resistance heating element. There is a method of controlling by transmitting to the radiator, but examples of the radiator include copper, stainless steel, nickel, and various ceramics.

In the present invention, a heat transfer body of 60 ° C. or more and 150 ° C.
Radiating objects having the above reflection temperatures may be combined. or,
You may combine the conventional warm air of 60 degrees C or less.

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

(1) Deodorizing device: JP-A-64-37560
No. 544 (2), upper left column to page 545 (3), upper left column.

(2) Washing water regenerating purifying agent and apparatus: JP-A-6-250352, page (3), “0011” to page (8), “0058”.

(3) Waste liquid treatment method: JP-A-2-6463
No. 8, 388 (2) lower left column to 391 (5) lower left column.

(4) Rinse bath between the developing bath and the fixing bath: JP-A-4-313949, page (18), “0054” to (2)
1) Page "0065".

(5) Water replenishment method: JP-A-1-28144
No. 6, page 250 (2), lower left column to lower right column.

(6) Method for controlling the drying air of an automatic developing machine by detecting the outside air temperature and humidity: JP-A-1-315745.
6 (2) lower right column to 501 (7) lower right column and JP-A-2-108051, 588 (2) lower left column to 589
(3) The lower left column of the page.

(7) Method for recovering silver from fixing waste liquid:
No. 27623, page (4) “0012” to page (7) “00”
71 ".

[0120]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Silver Halide Emulsion A) Using a simultaneous mixing method, a mixing temperature of 45 ° C., a pH of 3.0, and a silver potential (EAg) of 120 mV
, An aqueous silver nitrate solution and a halide solution composed of NaCl and KBr (molar ratio 7: 3) were simultaneously mixed. At this time, K ₂ [RhCl ₅ (H
₂ O)] was added at 1 × 10 ^-7 mol. The resulting emulsion was a monodisperse (coefficient of variation: 10%) silver chlorobromide (70 mol% silver chloride, 30 mol% silver bromide) cubic emulsion having an average particle size of 0.20 μm. Then, a modified gelatin described in JP-A-2-280139 (in which an amino group in gelatin is substituted with phenylcarbamyl, for example, JP-A-2-280139)
No. 287 (3), Exemplified compound G-8). The EAg of the obtained emulsion was 177 mV at 40 ° C., pH
Was 5.6. Thereafter, at 40 ° C., sodium p-toluenesulfonylchloramide trihydrate (chloramine T)
Was added at 90 mg per silver mole.

The obtained emulsion was reacted with 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene at a concentration of 60 mg per mol of silver and 100 mg of KBr, and then reacted with inorganic sulfur (S) dissolved in methanol. ₈ ) Water was added to the mixture and precipitated to an average particle size of 0.5 μm.
mg and 6 mg of chloroauric acid and added at a temperature of 60 ° C.
Chemical ripening was performed for 0 minutes. Thereafter, 400 mg of 4-hydroxy-6methyl-1,3,3a, 7-tetrazaindene and 100 mg of potassium iodide were added per mole of silver. After cooling to 40 ° C., 200 mg of sensitizing dye S-1 was added per 1 mol of silver, and the pH was adjusted to 5.1 with citric acid.

(Preparation of Other Silver Halide Emulsions) Emulsions shown in Table 2 were prepared by changing the mixing temperature, the amount of doped metal, the chemical ripening time, and the amount of sensitizing dye S-1 in the same manner as for silver halide emulsion A. I got

<Measurement of Emulsion Sensitivity of Silver Halide Emulsion> The above-obtained silver halide emulsion was coated in a single layer so as to have the following amounts, and the resulting film was dried with tungsten flash light through a 633 nm interference filter. Wedge exposure was performed for 7 × 10 ⁻⁷ seconds. Thereafter, the developed sample was subjected to a developing treatment, and the blackening density of the developed sample was measured with a PDA-65 (Konica Digital Densitometer) to determine the sensitivity of the silver halide emulsion. The sensitivities shown in Table 2 were expressed as relative sensitivities with an exposure amount of 100 at which silver halide emulsion A gave a density of 3.

Em coating solution for measuring emulsion sensitivity Silver halide emulsion Silver amount 3.0 g / m ² equivalent Gelatin 3.0 g / m ² Hydroquinone 50 mg / m ² 1-phenyl-4-hydroxymethyl-4-methyl-3 Pyrazolidone 5 mg / m ² sodium-isoamyl-n-decylsulfosuccinate 12 mg / m ² sodium polystyrene sulfonate 15 mg / m ² (Preparation of hydrazine derivative-adsorbed emulsion) And stirred for 30 minutes.

At this time, after the emulsion was decomposed by actinase, the emulsion was precipitated by a centrifugal separator, and the supernatant was quantified for the hydrazine derivative by HPLC (high performance liquid chromatography). Only the following were detected, and it was confirmed that the hydrazine derivative substantially added was adsorbed on the emulsion.

(Preparation of silver halide photographic light-sensitive material) These emulsions were mixed as shown in Table 4 and coated according to the following formulation to obtain an amount.

On a support, the following UC layer, Em layer, MC
Layer and Pro layer were applied in the order of 4 layers, and after cooling set at 5 ° C., the BC layer and BCPro layer were applied in the order of BC layer on the opposite side of the support, and after cooling set, both surfaces were simultaneously dried to obtain a sample. .

UC layer Gelatin 0.3 g / m ² Polymer latex L1 (particle size 0.08 μm) 0.1 g / m ² Sodium-isoamyl-n-decylsulfosuccinate 5 mg / m ² Hydroquinone 0.3 g / m ² Sterilization Agent Z 0.5 mg / m ² Solid disperse dye D-1 (average particle size 0.2 μm) 0.1 g / m ² Em layer Silver halide emulsion (Table 4) Silver amount 3.0 g / m ² equivalent amount Gelatin 1 2.0 g / m ² Mercaptopyrimidine 5 mg / m ² Polymer latex L1 (particle size 0.08 μm) 0.5 g / m ² Colloidal silica 75% by weight, vinyl acetate 12.5% by weight Vinyl pivalate 12.5% by weight suspension Pollution polymer ^{0.8g / m 2 SU-1 15mg} / m 2 sodium ethylenediaminetetraacetate 50 mg / m ² of polystyrene sulphonic acid ^{15mg / m 2 H-1 30mg} / m 2 M Layer Gelatin 0.5 g / m ² Dextrin (average molecular weight: ^{40,000) 0.3g / m 2 Na-21} 12mg / m 2 Pro Layer Gelatin 0.6 g / m ² 2-mercapto-6-hydroxy-purine 5 mg / m ² Sodium - di normal hexyl sulfosuccinate ^{8mg / m 2 SU-2 20mg} / m 2 SU-3 5mg / m 2 colloidal silica (average particle size ^{0.05μm) 0.5g / m 2 H-} 2 40mg / m 2 fungicides Z 0.5 mg / m ² BC layer Gelatin 1.5 g / m ² Polymer latex L3 0.3 g / m ² Colloidal silica (average particle size 0.05 μm) 100 mg / m ² Dye f1 40 mg / m ² Dye f2 7 mg / m ² dye f3 60 mg / m ² 1-phenyl-5-mercaptotetrazole 10 mg / m ² H-1 100 mg / m ² ethylenediaminetetraacetic acid 50 mg / M ² BCPro layer Gelatin 1.0 g / m ² Matting agent: monodispersed polymethyl methacrylate having an average particle size of 5 μm 50 mg / m ² average particle size 3 μm amorphous silica 12.5 mg / m ² dye f1 40 mg / m ² dye f2 7 mg / m ² dye ^{f3 60mg / m 2 H-2} 50mg / m 2 H-3 55mg / m 2 sodium - di normal hexyl sulfosuccinate 6 mg / sodium m ² of polystyrene sulphonic acid 10 mg / m ² KI 15 mg / ^{m 2}

[0130]

[Table 2]

[0131]

[Table 3]

[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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(Processing conditions) Developing time 38 ° C. 15 seconds Fixing time 38 ° C. 10 seconds Rinse time Normal temperature 8 seconds Drying time 50 ° C. 15 seconds (Developer composition) Diethylene triamine pentaacetic acid / pentasodium salt 1.45 g per liter of working solution S 0.85 g sodium sulfite 42.5 g potassium sulfite 17.5 g potassium carbonate 55 g sodium erythorbate 45 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-mercapto Adenine 0.07 g Sulfuric acid was added in such an amount that the working solution became pH 9.8.

(Fixing solution composition) Ammonium thiosulfate (70% aqueous solution) per liter of working 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) The pH of the used solution was adjusted to 4.9 with 25 ml of sulfuric acid.

Measurement of Sample Sensitivity The obtained sample was subjected to wedge exposure for 0.7 × 10 ⁻⁷ seconds with tungsten flash light through a 633 nm interference filter, and was automatically developed using a developer and a fixer of the above composition. Treated with a GR-26SR machine (manufactured by Konica Corporation) under the following conditions. PDA on the obtained developed sample
The blackening density was measured with -65 (Konica Digital Densitometer). The sensitivity is such that the sample 101 gives an exposure amount
And expressed as relative sensitivity.

Maximum Blackening Density (Dmax) Exposure up to 10 times the exposure amount giving a density of 3 was given, and the density was measured with an X-rite 361T, and the maximum value was taken as (Dmax).

Gamma (γ) Gamma (γ) is represented by the tangent of the straight line obtained by connecting the densities 1.0 and 3.0 on the characteristic curve obtained from the step wedge image and the tangent of the X axis.

Black pot The unexposed coating sample was treated in the same manner as in the measurement of sensitivity.
Black pots were visually evaluated with a 00x loupe.

Rank 5 has no black spots. Rank 4 has slight black spots of 10 μm or less, but has no practical problem. Rank 3 has slight black spots of 10 μm or more. No problem: Rank 2 has many black spots of 10 μm or more. Rank 1 has black spots of 10 μm or more on one surface.

Blackening pressure The obtained sample was subjected to a surface property measuring device Tribogear TYPE14 type DR manufactured by Shinto Kagaku Co., Ltd. in an environment of 23 ° C. and 40% RH.
Using a diamond scratching needle having a tip Rmm of 0.025 at a stage moving speed of 600 mm / min.
After applying a load of 0 g, the same treatment as in sensitometry was performed, and the blackening pressure at that time was visually evaluated.

Rank 5: No occurrence at all Rank 4: Light blackening pressure occurred at less than 10% of the portion where the load was applied Rank 3 Light blackening pressure occurred at less than 30% of the portion at which the load was applied Rank 2 Thin blackening pressure Occurs in less than 50% of the loaded part Rank 1 Light blackening pressure occurs in more than 50% of the loaded part

[0148]

[Table 4]

The sample according to the present invention (sample Nos. 106 to 1)
16) is better in black spots and blackening pressure.

Example 2 30 L of the developing solution of Example 1 was placed in a container having an opening area of 1 m ² and left without a lid for 2 weeks. At this time, the evaporated water was corrected to prepare a pseudo-oxidized liquid. This was placed in the automatic processing machine of Example 1, processed under the following developing conditions, and the sensitivity and gamma (γ) were measured by the method of Example 1.

Process 1: Developing time 30 seconds Process 2: Developing time 20 seconds Process 3: Developing time 15 seconds Process 4: Developing time 12 seconds

[0152]

[Table 5]

As can be seen from the results, not only the sensitivity and the high contrast property of the ordinary film are not sufficient, but also the sensitivity and the high contrast property of the oxidized fatigue solution are greatly deteriorated in the region where the developing time is short. In the image forming method of (1), the developing time is 2
It can be seen that even in the region of less than 0 seconds, the performance deterioration due to the oxidizing fatigue liquid is small.

Example 3 In the preparation of the sample 107 of Example 1, the addition position of the hydrazine derivative in the preparation of the emulsion B-500 was AD
-1 to AD-3. After preparing a coating solution using an emulsion in which the hydrazine derivative was added at a different position, the time until coating was changed to 1 hr and 8 hr at 35 ° C., and the sensitivity and black pot were measured as in Example 1.

AD-1: Sensitizing dye S-1 after completion of chemical ripening
10 minutes before addition AD-2: 10 minutes after addition of sensitizing dye S-1 AD-3: After addition of sensitizing dye S-1, refrigerated, redissolved, and added before A-250 mixing

[0156]

[Table 6]

As can be seen from the results, when the hydrazine derivative is added at the end of the chemical ripening, the stability of the coating solution during stagnation is excellent.

[0158]

According to the present invention, it is possible to provide a light-sensitive material having high contrast and high stability in an extremely short exposure time, a method for producing the light-sensitive material, and a rapid and highly productive image forming method. .

Claims (8)

[Claims] In a silver halide photographic material having at least one silver halide emulsion layer on one side of a support, two or more silver halide emulsions having different hydrazine derivative adsorption amounts are used. A silver halide photographic light-sensitive material comprising: 2. The silver halide photographic material according to claim 1, wherein the silver halide emulsion having a large amount of hydrazine derivative adsorbed thereon has low sensitivity. 3. The average particle size of silver halide grains in a silver halide emulsion having a large amount of adsorption of a hydrazine derivative is smaller than the average particle size of silver halide particles in a silver halide emulsion having a small amount of adsorption of a hydrazine derivative. The silver halide photographic light-sensitive material according to claim 1 or 2, wherein 4. A silver halide emulsion having a larger amount of hydrazine derivative adsorbed than a silver halide emulsion having a smaller amount of hydrazine derivative adsorbed on a silver halide grain by a transition metal belonging to Groups 6 to 10 of the periodic table. 4. The silver halide photographic light-sensitive material according to claim 1, wherein the content is large. 5. The transition metal of Groups 6 to 10 of the periodic table is Rh,
5. The silver halide photographic material according to claim 4, wherein the material is Ru, Re, or Os. 6. A development time of the silver halide photographic material of claim 1, 2, 3, 4 or 5 after imagewise exposure.
An image forming method, wherein an image is obtained by performing development in less than seconds, followed by fixing, washing and drying. 7. The image forming method according to claim 6, wherein the exposure time of the silver halide photographic material is less than 10 ^-6 seconds. 8. A silver halide photographic material having at least one silver halide emulsion layer on one side of a support, wherein two or more silver halide emulsions having different hydrazine derivative adsorption amounts are used. A method for producing a silver halide photographic light-sensitive material, characterized by adding a hydrazine derivative at the end of chemical ripening.