JPH08286333A - Processing method for silver halide photosensitive material - Google Patents

Abstract

PURPOSE: To provide an image with high sensitivity, low fog, contrasty, and high quality by use of a developer with no environmental pollution by processing with a specified developing solution. CONSTITUTION: A photosensitive material containing a hydrazine derivative and a compound represented by formula I or II in a silver halide emulsion layer and/or its adjacent layer is processed with a developing solution which contains practically no dihydroxybenzene family, contains a developer represented by formula III, and satisfies the following condition. The developer represented by formula III and auxiliary processing agent realizing superadditivity are contained, 0.6 mole/litter or less carbonate is contained, and when KOH of 0.1 mole per one litter of developing solution is added, pH variation is 0.1-0.45, and when H2 SO4 of 1 mole is added, pH variation is 0.1-0.5. In formulas I, II, R1 -R3 represent a hydrogen atom or an alkyl group, R4 represents a hydrogen atom, an alkinyl group, and Ar represents an aromatic group, a heterocyclic group. In formula III, R5 , R6 represented an alkyl group, an amino group, k represents 0 or 1, and when k is 1, X represents -CO- or -CS-.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more specifically, a developer having no environmental deterioration can be used to obtain a high-sensitivity, low-fog and high-contrast image with high quality. The present invention relates to a method for processing a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, environmental problems have become serious around the world, and from the standpoint of environmental protection, the research and development of products and systems with excellent environmental suitability are being actively pursued in each industry. is there. The printing industry is no exception, for example, with regard to developing waste liquid for obtaining printed manuscripts,
Since the dumping of waste liquid into the ocean is also prohibited from January 1996,
There is an urgent need for improvement.

Conventionally, a method of using ascorbic acid as a developing agent as a developer having excellent environmental suitability has been disclosed in, for example, US Pat. No. 5,236,816.

However, when ascorbic acid is used as a developing agent, the developing property becomes inactive and high sensitivity cannot be obtained, as compared with the conventional developing agents.

For the purpose of increasing the sensitivity, means for increasing the amount of the ascorbic acid main agent and auxiliary developer and reducing the amount of the inhibitor can be considered, but no effective means for obtaining a satisfactory developing performance has been proposed yet.

The above-mentioned US Pat. No. 5,236,816 discloses that sensitivity is increased by increasing the amount of carbonate in combination with ascorbic acid.
However, as a result of repeating the method, it was found that the technique had a drawback of significantly increasing fog and deteriorated the reproducibility of halftone dot originals, particularly the omission of large dots, and did not reach a practical level,
Further improvements were desired.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining a high-sensitivity, low-fog and high-contrast image with high quality by using a developer which does not deteriorate the environment. It is to provide a processing method.

[0008]

The above objects of the present invention have been achieved by the following present invention.

Silver halide containing at least one hydrazine derivative and at least one selected from the compounds represented by the following general formula [1] or [2] in the silver halide emulsion layer and / or its adjacent layer. In the processing method of a photographic light-sensitive material, the developer contains substantially no dihydroxybenzenes, contains a developer represented by the following general formula [3], and satisfies the following conditions (1) to (4): A method of processing a silver halide photographic light-sensitive material, which comprises processing with a developing solution to be filled.

[0010]

[Chemical 4]

In the formula, R ₁ , R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group or a substituted aryl group. R ₁ , R ₂ and R ₃ may form a ring.

[0012]

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In the formula, Ar represents a substituted or unsubstituted aromatic group or heterocyclic group. R ₄ represents a hydrogen atom, an alkyl group, an alkynyl group, or an aryl group, and Ar and R ₄ may be connected by a connecting group to form a ring.

[0014]

[Chemical 6]

In the formula, R ₅ and R ₆ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group or R ₅ And R ₆ may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X represents -CO- or -CS-.

(1) Contain at least one developer of the above-mentioned general formula [3] and an auxiliary developer exhibiting super-chemical conversion. (2) Contain 0.6 mol / liter or less of a carbonate. (3) The pH fluctuation due to addition of 0.1 mol of KOH per liter of developer is 0.1 to 0.45. (4) Addition of 0.1 mol of H ₂ SO ₄ per liter of developer. The resulting pH fluctuation is 0.1 to 0.5.

The present invention will be described in detail below.

The hydrazine compound used in the silver halide emulsion layer and / or its adjacent layer of the present invention includes compounds represented by the following general formula [H].

[0019]

[Chemical 7]

The general formula [H] will be described in detail below.

In the formula, A ₀ represents an aliphatic group, an aromatic group or a heterocyclic group. The aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, and is particularly a straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms. Examples thereof include a methyl group, an ethyl group, a t-butyl group, an octyl group, a cyclohexyl group, and a benzyl group. These are further suitable substituents (for example, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, Sulfoxy group, sulfonamide group, sulfamoyl group, acylamino group, ureido group, etc.).

The aromatic group represented by A ₀ in the general formula [H] is preferably a monocyclic or condensed ring aryl group, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by A ₀ in the general formula [H] is preferably a monocyclic or condensed ring heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen, for example, a pyrrolidine ring. , Imidazole ring, tetrahydrofuran ring, morpholine ring, pyridine ring, pyrimidine ring, quinoline ring, thiazole ring, benzothiazole ring, thiophene ring and furan ring.

Particularly preferred as A ₀ are an aryl group and a heterocyclic group. The aromatic group and heterocyclic group represented by A ₀ preferably have a substituent. Preferred substituents include, for example, alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, substituted amino groups, acylamino groups, sulfonylamino groups, ureido groups, urethane groups, aryloxy groups, sulfamoyl groups, carbamoyl groups, Alkylthio group, arylthio group, sulfothio group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide Examples thereof include a group, a carboxy group and a phosphoric acid amide group, and these groups may be further substituted. Among these substituents, when a developer having a pH of 10.5 or less is used and a total processing time (Dry to Dry) is 60 seconds or less, a substituent having an acidic group with a pKa of 7 to 11 is selected. Preferred are specifically, sulfonamide group, hydroxy group and mercapto group, and particularly preferred is sulfonamide group.

Further, A ₀ preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. As the anti-diffusion group, a ballast group commonly used in a non-moving photographic additive such as a coupler is preferable, and as the ballast group, an alkyl group or an alkenyl group having 8 or more carbon atoms and relatively inert to photographic properties is preferable. , An alkynyl group, an alkoxy group,
Examples thereof include a phenyl group, a phenoxy group and an alkylphenoxy group.

As the silver halide adsorption promoting group, thiourea, thiourethane group, mercapto group, thioether group,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorbing group described in JP-A No. 64-90439.

B ₀ represents a blocking group, preferably-
G ₀ −D ₀ .

G ₀ is a --CO-- group, --COCO-- group, --CS-- group,
_{-C (= NG 1 D 1)} - group, -SO- group, -SO ₂ - group or -P (O)
Represents a (G ₁ D ₁ )-group. G ₁ is a simple bond, -O- group, -S
- group or a -N (D ₁₎ - represents a group. D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and a plurality of D's are present in the molecule.
_{If one} is present they may be the same or different.

D ₀ represents an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group or a mercapto group. Preferred G ₀ is -CO- group, -COCO- group, particularly preferably -C.
An OCO- group can be mentioned. Preferred D ₀ is a hydrogen atom,
Examples thereof include an alkoxy group and an amino group.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group ( Etoxaryl etc.)

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

[0032]

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[0033]

[Chemical 9]

[0034]

[Chemical 10]

[0035]

[Chemical 11]

[0036]

[Chemical 12]

The compounds represented by the general formulas [1] and [2] used in the present invention are nucleation accelerators which are used for effectively promoting the contrast increase by the hydrazine derivative.

In the above general formula [1], R ₁ , R ₂ and R
₃ 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. A ring can be formed by R ₁ , R ₂ and R ₃ . 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 molecular weight of 300 or more is more preferable. Further, as preferable adsorption groups, heterocycle, mercapto group, thioether group,
Examples thereof include thione group and thiourea group.

Specific examples of the compound of the general formula [1] which is a nucleation accelerator will be given below.

[0040]

[Chemical 13]

[0041]

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[0042]

[Chemical 15]

As a more preferred embodiment of the above general formula [1], a compound represented by the following general formula [1A] can be mentioned.

[0044]

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In the general formula [1A], R ^{1 to} R ⁴ are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group,
It represents a substituted or unsubstituted aryl group, a saturated or unsaturated heterocycle. These can be linked together to form a ring. Further, each pair of R ¹ , R ² and R ³ , R ⁴ is not a hydrogen atom at the same time.

X represents an S, Se or Te atom. L ¹ and L ²
Represents a divalent linking group. Specifically, combinations of the groups shown below and appropriate substituents thereof (for example, an alkylene group, an alkenylene group, an arylene group, an acylamino group,
Groups having a sulfonamide group).

-CH2-, -CH = CH-, -C2H4-, pyridinediyl, -N (Z ₁ )-, (Z ₁ represents a hydrogen atom, an alkyl group or an aryl group), -O-, -S -, - (CO) -, - (SO 2) -, - CH 2 N-,
Further, it is preferable that at least one of the following structures is included in the linking group.

-[CH ₂ CH ₂ O]-,-[C (CH ₃ ) HCH ₂ O]-,-[O
C (CH ₃ ) HCH ₂ O]-,-[OCH ₂ C (OH) HCH ₂ ]-Next, in the general formula [2], Ar represents a substituted or unsubstituted aromatic group or heterocyclic group. R ₄ is a hydrogen atom, an alkyl group,
It represents an alkynyl group or an aryl group, and Ar and R ₄ 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.
Further, a preferable silver halide adsorbing group is represented by the general formula [H]
And a group having the same meaning as the silver halide adsorbing group of the compound represented by.

Next, specific examples of the compound represented by the general formula [2] will be given.

[0050]

[Chemical 17]

[0051]

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The compound represented by the general formula [3] used in the present invention is preferably a compound represented by the following general formula [3-a] in which R ₅ and R ₆ are bonded to each other to form a ring.

[0053]

[Chemical 19]

In the above general formula [3-a], R ₇ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group or an amide. Group, a sulfonamide group, Y ₁ represents O or S, Y ₂ represents O, S or N
Represents R ₈ . R ₈ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

The alkyl group in the above general formula [3] or [3-a] is preferably a lower alkyl group, particularly preferably an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group or lower alkyl group. An amino group substituted with a group is preferable, a lower alkoxy group is preferable as the alkoxy group, a phenyl group or a naphthyl group is preferable as the aryl group, and these groups may have a substituent and may be substituted. Examples of the posable group include a hydroxy group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, a sulfonamide group and the like as a preferable substituent.

Next, specific examples of the compound of the developer represented by the general formula [3] or [3-a] according to the present invention will be shown by the groups of the general formulas, but the present invention is not limited thereto. It is not something that will be done.

[0057]

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[0058]

[Chemical 21]

These compounds are typically ascorbic acid or erythorbic acid or their derivatives,
It can be obtained as a commercial product or can be easily synthesized by a known synthesis method.

Examples of the auxiliary developer exhibiting superadditivity with the developer represented by the general formula [3] include 3-pyrazolidone derivatives and p-aminophenol derivatives. However, the auxiliary developer exhibiting superadditivity with the developer represented by the general formula [3] is not limited to these. These compounds are conventionally well known as auxiliary developers.
Specific examples of the compound will be shown below, but the invention is not limited thereto.

1-phenyl-3-pyrazolidone 1-phenyl-4,4'-dimethyl-3-pyrazolidone 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1-phenyl-5-methyl-3- Pyrazolidone 1-p-aminophenyl-4,4'-dimethyl-3-pyrazolidone 1-p-tolyl-4,4'-dimethyl-3-pyrazolidone 1-p-tolyl-4-methyl-4-hydroxymethyl-3 -Pyrazolidone N-methyl-p-aminophenol N- (β-hydroxyethyl) -p-aminophenol N- (4-hydroxyphenylethyl) glycine 2-methyl-p-aminophenol p benzylaminophenol In the present invention, development The liquid or treatment agent is characterized in that it does not substantially contain a dihydroxybenzene-based developer. The dihydroxybenzene-based developer mentioned here is a compound represented by the following general formulas V-1 to V-3.

[0062]

[Chemical formula 22]

In the above formula, R _{5 to} R ₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, a carboxyl group, a halogen atom or a sulfo group.

Specific examples of compounds include, for example, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethyl. Among them are hydroquinone, but the most commonly used one is hydroquinone.

In the present invention, these dihydroxybenzenes are not substantially contained. The term "substantially none" as used herein refers to a substance that is contained in a small amount to the extent that an allergic effect or a developing effect is not expressed, but in the present invention, a substance that does not contain at all is preferable.

In the present invention, the carbonate content of the developing solution is 0.6 mol / liter or less, and further 0.3 to
It preferably contains 0.45 mol / liter.

In the present invention, the fluctuation of the pH of the developing solution means the buffering ability of the developing solution with respect to acid and alkali, and the increase of the pH by adding 0.1 mol of KOH per liter of the developing solution is 0. 0.1 to 0.45 and by adding 0.1 mol of H ₂ SO ₄ per liter of developer.
The pH drop is 0.1-0.5.

Furthermore, the increase in pH by adding 0.1 mol of KOH per liter of the developing solution is 0.1 to 0.
35 and 0.1 H ₂ SO ₄ per liter of developer.
The decrease in pH due to the addition of moles is preferably 0.1 to 0.4.

This cannot be achieved with a carbonate amount of 0.6 mol / liter or less, but a so-called pH buffering agent (eg, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine) or the like is used in combination. This can be easily achieved by doing. The pH buffering agent mentioned here is a compound having a pH buffering ability, and is not limited to the above-mentioned compounds.

The silver halide photographic light-sensitive material used in the present invention preferably has at least one conductive layer on the support. As a typical method for forming the conductive layer, there are a method using a water-soluble conductive polymer, a hydrophobic polymer and a curing agent, and a method using a metal oxide. For these methods, see, for example, JP-A-3-265842.
The methods described on pages (5) to (15) can be used.

The silver halide emulsion of the silver halide photographic light-sensitive material according to the present invention includes, for example, silver bromide, silver iodobromide,
Although any of those used for ordinary silver halide emulsions such as silver iodochloride, silver chlorobromide and silver chloride can be used, silver chlorobromide containing 50 mol% or more of silver chloride or It is silver chloride.

Further, it was determined from the grain size of silver halide grains measured by an electron micrograph (standard deviation of grain size).
Monodisperse particles having a coefficient of variation represented by / (average value of particle size) × 100 of 15% or less are preferable.

Various techniques and additives known in the art can be used in the silver halide emulsion of the present invention. For example,
The silver halide photographic emulsion and backing layer used in the present invention include various chemical sensitizers, toning agents, hardeners, surfactants, thickeners, plasticizers, sliding agents, development inhibitors, and ultraviolet absorbers. , An anti-irradiation dye, a heavy metal, a matting agent and the like can be further contained by various methods. Further, a polymer latex can be contained in the silver halide photographic emulsion and the backing layer of the present invention.

Details of these additives are described in Research Disclosure (RD) No. 17643 (December 1978) and the same.
No.18716 (November, 1979), the relevant parts are summarized below.

Additive Type (RD) 17643 (RD) 18716 1. Chemical sensitizer Page 23 Page 648 Right column 2. Sensitivity enhancer Same as above 3. Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4. Whitening agent Page 24 5. Antifoggants and stabilizers 24 to 25 pages 649 right column 6. Light absorbers, filter dyes 25 to 26 pages 649 right column ~ ultraviolet absorbers 650 page left column 7. Anti-stain agent page 25 right column page 650 left-right column 8. Dye image stabilizer page 25 9. Hardener 26 pages 651 left column 10. Binder page 26 Same as above 11. Plasticizer, lubricant Page 27 Page 650 Right column 12. Coating aid, surface active agent, pages 26 to 27, same as above 13. Antistatic agent page 27 Same as above As the support that can be used in the silver halide photographic light-sensitive material of the present invention, cellulose acetate, cellulose nitrate,
Examples thereof include polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, paper coated with polyolefin, glass and metal. These supports are subjected to a surface treatment if necessary.

In the processing method of the present invention, as a silver sludge inhibitor in the developing solution, for example, JP-B-62-4702, JP-A-3-51844, 4-26838, 4-362942, 1- 3190
The compounds described in No. 31 and the like can be used.

Further, the waste developer can be regenerated by energizing it. Specifically, a cathode (for example, an electric conductor or semiconductor such as stainless steel wool) is put in the developing waste liquid, and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) is put in the electrolyte solution, and the anion exchange membrane is used. The developer waste solution tank and the electrolyte solution tank are brought into contact with each other via the, and both electrodes are energized for regeneration. It is also possible to process the light-sensitive material according to the present invention while energizing. At that time, various additives added to the developer, for example, preservatives, alkali agents, pH buffers, sensitizers, antifoggants, silver sludge inhibitors, etc., which can be added to the developer, are additionally added. You can do it. Further, there is a method of processing the light-sensitive material while energizing the developing solution, and at that time, an additive which can be added to the developing solution as described above can be additionally added. When the developer waste liquid is regenerated and used, transition metal complex salts are preferable as the developing agent of the developer used.

Examples of the sulfite or metabisulfite used as a preservative in the treatment method of the present invention include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. Sulfite is 0.25 mol /
It is preferably liter or more. It is particularly preferably 0.4 mol / liter or more.

In the developer, if necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.) , Solubilizers (eg polyethylene glycols, their esters, 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, etc.), chelating agents (For example, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), development accelerator (for example, US Pat. No. 2,304,025)
Nos. 5,047,456 and Japanese Patent Publication No. 47-45541), a hardener (eg glutaraldehyde or its bisulfite adduct), an antifoaming agent and the like can be added. In order to keep the total processing time (Dry to Dry) at 60 seconds or less, the pH of the developing solution is preferably adjusted to 8.5 to 10.5.

The compounds of the present invention, as a special form of development processing, include a developing agent in a light-sensitive material, for example, an emulsion layer,
You may use it for the activator processing liquid which makes a photosensitive material process in alkaline aqueous solution and develops. Such a developing treatment is often used as one of the rapid processing methods for a light-sensitive material in combination with a silver salt stabilizing treatment with a thiocyanate, and can be applied to such a processing solution.
In the case of such rapid processing, the effect of the present invention is particularly great.

As the fixing solution, those having a generally used composition can be used. The fixing solution is generally an aqueous solution containing a fixing agent and others, and the pH is 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 capable of forming a soluble stable silver complex salt. A compound known as a fixing agent can be used.

A water-soluble aluminum salt which acts as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum, etc. can be added to the fixing solution.

If desired, the fixer may contain preservatives (eg, sulfite, bisulfite), pH buffer (eg, acetic acid), and p.
Compounds such as an H-adjusting agent (for example, sulfuric acid) and a chelating agent capable of softening water can be included.

The developing solution may be a mixture of fixed components, an organic aqueous solution containing glycol or amine, or a viscous liquid with a high viscosity in a semi-kneaded state. Further, it may be diluted before use, or may be used as it is.

In the development processing of the present invention, the development temperature is
It can be set to a normal temperature range of 20-30 ° C,
It can also be set to a high temperature treatment range of 30 to 40 ° C.

The black-and-white light-sensitive material according to the present invention is preferably processed using an automatic processor. At that time, the processing is performed while replenishing a fixed amount of developing solution proportional to the area of the photosensitive material. The development replenishment amount is 1 in order to reduce the amount of waste liquid.
Not more than 300 ml per m ² . Preferably 75 to ² per m ²
It is 00 ml.

According to the present invention, in order to shorten the developing time, the total processing time (Dry to Dry) from when the leading edge of the film is inserted into the automatic developing machine to when it comes out of the drying zone is 10 when the processing is performed by using the automatic developing machine. It is preferably -60 seconds. The total processing time referred to here includes all process times required for processing the black-and-white light-sensitive material, and specifically, for processing, for example, developing, fixing, bleaching, washing, stabilizing, drying, etc. It is the time that includes all the process time, that is, the time to Dry to Dry. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dr
y to Dry) is 15 to 50 seconds.

In the automatic processor, a heat transfer material having a temperature of 90 ° C. or higher (for example, a heat roller at 90 ° C. to 130 ° C.) or 150
Radiant objects above ℃ (for example, tungsten, carbon, nichrome, mixture of zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc. to generate heat and radiate heat directly, or heat energy from resistance heating element to copper, stainless steel, nickel, various Those that emit infrared radiation by transmitting heat to a radiator such as ceramic) and those that have a drying zone are included.

The hydrazine derivative and the compounds of the general formulas [1] and [2] used in the present invention can be used in any layer on the silver halide emulsion layer side, but are preferably a silver halide emulsion layer or It is preferably used for the adjacent layer. The addition amount is the grain size, composition,
The optimum amount varies depending on the degree of chemical sensitization and the type of inhibitor, but generally 10 ^-6 to 1 per mol of silver halide.
It may be in the range of 0 ^-1 mol, and 10 ^-5 to 10 ^-2 mol is particularly preferable.

[0090]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto.

Example 1 <Preparation of Light-Sensitive Material> (Preparation of Silver Halide Emulsion A) A salt of silver chloride 70 mol% and a balance of silver bromide having a mean thickness of 0.05 μm and a mean diameter of 0.15 μm, prepared by the simultaneous mixing method. A silver bromide core grain was prepared. When mixing the core particles, K ₃ RuCl ₆ was added at 8 × 10 ^-8 mol per mol of silver. The core particles were shelled using the double-blending method. At that time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ^-7 mol per mol of silver.

The resulting emulsion had a thickness of 0.10 μm and a mean diameter of 0.25 μm, and was a core / shell type monodisperse (variation coefficient of 10%) (100) plane as the principal plane of silver chloroiodobromide (silver chloride 90
The emulsion was a tabular grain composed of mol%, silver iodide 0.2 mol% and the rest silver bromide. Then, it was desalted using the modified gelatin described in JP-A-2-280139 (Exemplary compound G-8 in which the amino group in gelatin was substituted with phenylcarbamyl). The EAg after desalting was 190 mv at 50 ° C.

The resulting emulsion was treated with 4-hydroxy-6-methyl-1,
The pH of 3,3a, 7-tetrazaindene was added by adding 1 × 10 ^-3 mol per mol of silver, and further adding potassium bromide and citric acid.
After adjusting to 5.6, EAg123mv and adding 2 × 10 ^-5 mol of chloroauric acid, 3 × 10 ^-6 mol of inorganic sulfur was added and chemical ripening was performed at a temperature of 60 ° C. until maximum sensitivity was obtained.

After aging, 4-hydroxy-6-methyl-1,3,3
2 × 10 ⁻³ mol of a, 7-tetrazaindene per mol of silver,
3 × 10 ^-4 mol of 1-phenyl-5-mercaptotetrazole and gelatin were added.

(Preparation of silver halide emulsion B) 60 mol% of silver chloride, 1.5 mol% of silver iodide, the rest of which is silver bromide, having an average thickness of 0.05 μm and an average diameter of 0.15 μm. A silver bromide core grain was prepared. K ₃ Rh (H
₂ O) Br ₅ was added in an amount of 2 × 10 ^-8 mol per mol of silver. The core particles were shelled using the double-blending method. At that time
K ₂ IrCl ₆ was added in an amount of 3 × 10 ^-7 mol per mol of silver. The obtained emulsion was a core / shell type monodisperse (variation coefficient: 10%) silver chloroiodobromide (silver chloride 90%) having an average thickness of 0.10 μm and an average diameter of 0.42 μm.
The emulsion was a tabular grain composed of mol%, silver iodobromide 0.2 mol% and the rest silver bromide). Then, it was desalted using the above-mentioned G-8. The EAg after desalting was 180 mv at 50 ° C.

4-hydroxy-6-methyl-1, was added to the obtained emulsion.
A pH of 5.3 was obtained by adding 3,3a, 7-tetrazaindene to 10 ^-3 mol per mol of silver, and further adding potassium bromide and citric acid.
6. Adjust to EAg123mv and add 2 × 10 ^-5 mol of chloroauric acid, then add 3 × 10 ^-5 mol of N, N, N'-trimethyl-N'-heptafluoroselenourea and add 60 ° C to the temperature. The chemical aging was performed until the maximum sensitivity was obtained. After completion of ripening, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added 2 × per mol of silver.
10 ^-3 mol, 1-phenyl-5-mercaptotetrazole 3
× 10 ^-4 mol and gelatin were added.

(Preparation of silver halide photographic light-sensitive material for printing plate-making scanner containing hydrazine derivative) On one undercoat layer of a support, a gelatin undercoat layer of the following Formulation 1 was used in which the amount of gelatin was 0.5 g / m 2. at ^2, amount of silver 1.5 g / m ² of silver halide emulsion layers 1 formulation 2 thereon, gelatin amount
0.5 g / m ² and a coating solution of the following formulation 3 as an intermediate protective layer on the upper layer thereof so that the amount of gelatin is 0.3 g / m ² and a silver halide emulsion layer of the formulation 4 on the upper layer thereof. 2 so that the amount of silver was 1.4 g / m ² and the amount of gelatin was 0.4 g / m ^2, and a coating solution of the following formulation 5 was added to give a gelatin amount of 0.
Simultaneous multi-layer coating was performed so that the amount was 6 g / m ² . On the other side of the undercoat layer, a backing layer having the following formulation 6 with a gelatin content of 0.
As will become 6 g / m ^2, the hydrophobic polymer layer of the following formulation 7 thereon, further the amount of gelatin backing protective layer having the following composition 8 thereon the emulsion layer side so as to 0.4 g / m ² A sample was obtained by simultaneous multilayer coating.

Formulation 1 (Composition of gelatin subbing layer) Gelatin 0.5 g / m ² Exemplified dye a (ball-mill dispersed to a particle size of 0.1 μm) 25 mg / m ² Exemplified dye b (ball-mill dispersed to a particle size of 0.1 μm) 20 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² S-1 (sodium-iso-amyl-n-decylsulfosuccinate) 0.4 mg / m ² Formulation 2 (composition of silver halide emulsion layer 1) Halogen halide emulsion a silver amount 2.9 g / sensitizing dyes as m becomes ² d-1 6mg / m ² sensitizing dye d-2
3 mg / m ² hydrazine derivative H-7
30 mg / m ² amino compound Na-9 10 mg / m ² compound e 100 mg / m ² latex polymer f 1.0 g / m ² hardener g 5 mg / m ² S-1 0.7 mg / m ² 2-mercapto-6-hydroxy Purine 10 mg / m ² EDTA 50 mg / m ² Formulation 3 (intermediate layer composition) Gelatin 0.3 g / m ² S-1 2 mg / m ² Formulation 4 (silver halide emulsion layer 2 composition) Silver halide emulsion B Silver amount 0. 2 g / m sensitized at ² dye d-1 0.5mg / m ² redox compound ^{Re-1 4mg / m 2 S} -1 1.7mg / m 2 formulation 5 (emulsion protective layer composition) gelatin 0.6 g / m ² Dye c (ball mill-dispersed powder with a particle size of 0.1 μm) 40 mg / m ² S-1 12 mg / m ² Matting agent: Monodisperse silica with an average particle size of 3.5 μm 25 mg / m ² 1,3- Vinylsulfonyl-2-propanol 40 mg / m ² Surfactant h 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 10 mg / m ² Hardener g 30 mg / m ² Formulation 6 (backing layer composition) Gelatin 0.6 g / m ² S-15 mg / m ² latex polymer f
0.3 g / m ² colloidal silica (average particle size 0.05 μm) 70 mg / m ² Dye k 20 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² Compound i 100 mg / m ² Formulation 7 (polymer layer composition) Latex j ( Methyl methacrylate: Acrylic acid = 97: 3) 1.0g / m ² Hardener g 6mg / m ² Formulation 8 (Backing protective layer) Gelatin 0.4g / m ² Matting agent: Monodisperse polymethylmethacrylate 50mg with average particle size 5μm / m ² Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Surfactant h 1 mg / m ² H (OCH ₂ CH ₂ ) ₆₈ OH 50 mg / m ² Hardener g 20 mg / m ²

[0099]

[Chemical formula 23]

[0100]

[Chemical formula 24]

[0101]

[Chemical 25]

(Developer Composition) Developer 1 Diethylenetriamine pentaacetic acid (40% aqueous solution) 3.63 g Sodium sulfite 16 g KBr 7 g Potassium carbonate Amount shown in Table 1 Boric acid Amount shown in Table 8-Mercaptoadenine 0.07 g Sodium erythorbate 25 g Dimezone S 2g Benzotriazole 0.25g 1-Phenyl-5-mercaptotetrazole 0.03g Add water and potassium hydroxide to make 1 liter and adjust pH to 10.4.

Developer 2 Diethylenetriamine pentaacetic acid (40% aqueous solution) 3.63g Sodium sulfite 16g KBr 7g Potassium carbonate Amount shown in Table 3 Trisodium phosphate Amount shown in Table 8-Mercaptoadenine 0.07g Sodium erythorbate 25g Dimezone S 2g Benzo Triazole 0.25 g 1-phenyl-5-mercaptotetrazole 0.03 g Water and sulfuric acid were added to 1 liter to adjust the pH to 10.4 CFL-881 (manufactured by Konica Corporation) was used as a fixing solution.

<Processing conditions> (Processing) (Processing temperature [° C]) (Processing time [sec]) Development 35 30 Fixing 35 20 Washing with water at room temperature 20 Drying 50 10 <Evaluation of reproducibility of dot original and dot quality> Select set 2 of silver halide photographic light-sensitive materials prepared by the above method
5%, 50%, 95 with 000 (Agfar output machine)
% Net at 300 lines / inch, output at 3600 dpi, and after exposing while changing the light intensity, the automatic developing machine LD-220QT (manufactured by Dainippon Screen Co., Ltd.) was used with the above processing solution and processing conditions. Each sample was processed by using the same and the halftone% of the portion output to the halftone% was measured to evaluate the reproducibility.

<Evaluation method of halftone dot at midpoint> Midpoint at the exposure amount at which the halftone dot output at 5% reproduces 5% (target 50%)
The closer the finished net% to 50%, the better.

<Evaluation method for large dot halftone%> Similar to the evaluation of the midpoint halftone dot%, the halftone dot% at the midpoint (target 95%) is 90% in the exposure amount at which the halftone dot output at 5% reproduces 5%. The closer to%, the better.

<Evaluation method of halftone dot quality> The halftone dot quality (sharpness) was evaluated using a 100 times loupe at the midpoint (target 50%) at the exposure amount at which the halftone dot output at 5% reproduced 5%.
The highest rank is 5, and it is 4, 3, 2, 1 according to the dot quality.
And lowered the rank. Ranks 1 and 2 are practically unfavorable levels.

<Evaluation Method for Sensitivity and Fog> The silver halide photographic light-sensitive material prepared as described above was exposed to a helium-neon laser light intensity for 10 ⁻⁶ seconds in a wedge-like manner, and was subjected to the above processing solution and processing conditions. Processed. The density of the unexposed portion was measured to give a fog, and the reciprocal of the exposure amount giving a density of 4 was evaluated as the sensitivity. The sensitivities in the table are shown as relative sensitivities when the sensitivity of Sample No. 1 is 100. If the value is extremely low, it cannot be put to practical use. The results obtained are shown in Table 1.

[0109]

[Table 1]

As is apparent from Table 1, the sample of the present invention is superior in halftone dot quality to the comparative sample, and it is possible to obtain a silver halide photographic light-sensitive material having high sensitivity and low fog.

[0111]

According to the present invention, a method for processing a silver halide photographic light-sensitive material having high sensitivity, low fog and excellent halftone dot quality can be obtained by using an ascorbic acid type developer having good environmental suitability. I was able to.

Claims (1)

[Claims] 1. A halogen containing at least one hydrazine derivative and at least one compound selected from the compounds represented by the following general formula [1] or [2] in the silver halide emulsion layer and / or its adjacent layer. In the method of processing a silver halide photographic light-sensitive material, the developing solution contains substantially no dihydroxybenzenes, contains a developer represented by the following general formula [3], and has the following (1) to (4) A method of processing a silver halide photographic light-sensitive material, which comprises processing with a developer satisfying a condition. Embedded image In the formula, R ₁ , R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group and a substituted aryl group. R ₁ , R ₂ ,
R ₃ may form a ring. Embedded image In the formula, Ar represents a substituted or unsubstituted aromatic group or heterocyclic group. R ₄ represents a hydrogen atom, an alkyl group, an alkynyl group, or an aryl group, and Ar and R ₄ may be connected by a connecting group to form a ring. Embedded image In the formula, R ₅ and R ₆ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group or R
₅ and R ₆ may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X represents -CO- or -CS-. (1) It contains at least one kind of the above-mentioned developer of the general formula [3] and an auxiliary developer exhibiting super chemical conversion property. (2) Containing 0.6 mol / liter or less of carbonate (3) The pH fluctuation due to addition of 0.1 mol of KOH per liter of developer is 0.1 to 0.45. (4) The pH fluctuation due to addition of 0.1 mol of H ₂ SO ₄ per liter of the developer is 0.1 to 0.5.