JP3225382B2 - Developer composition for black-and-white silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel developer composition for a black-and-white silver halide photographic light-sensitive material, and more particularly to a developer composition for a black-and-white silver halide photographic light-sensitive material which does not cause silver stain even when subjected to rapid development processing. About things.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material for black and white, particularly a silver halide light-sensitive material for printing plate making, is generally prepared after imagewise exposure.
Photographic processing is performed in four processes of development, fixing, washing and drying. In photographic photosensitive materials for printing plate making,
A photographic technique capable of reproducing a super-high contrast image is used, and various photographic techniques are known.
A hydrazine derivative and a nucleation accelerator as found in JP-A 4-98239 are contained in a silver halide photographic light-sensitive material, and the pH is substantially less than 11 and described in JP-A-56-106244. There is known a method of processing with a developer containing no alkanolamine compound as described above. Many of these development processes are processed with a developer in which dihydroxybenzenes and 3-pyrazolidones or aminophenols are combined, but since the development is carried out in an alkali, oxidation of the developing agent is prevented to prevent storability. For the purpose of improvement, a sulfite is usually contained in the developer. However, since this sulfite has the property of dissolving silver salts, it dissolves silver salts during development from photographic light-sensitive materials, and the silver salts dissolved in the developing solution are reduced to metallic silver, which precipitates out and becomes photosensitive. It will adhere to the surface of the material and cause silver stains. In particular, silver contamination becomes a problem in high-temperature rapid processing using a transport type automatic developing machine.

Further, when the replenishing amount of the developing solution is smaller than the processing amount of the photosensitive material, the problem is serious because the deposition concentration is relatively increased. In order to solve this problem, studies have been made on compounds that improve the storage stability without dissolving the silver salt, but at present it has not been found yet. On the other hand, studies have been made on means for trapping dissolved silver salts to prevent precipitation. For example, the search for silver sludge inhibitors has been widely conducted, and US Pat. No. 3,173,789
JP-A-5-36029 discloses a disulfide compound, and JP-B-62-4702 discloses a 2-mercaptobenzimidazole sulfonic acid derivative. It has been reported. However, in the method using these, the developing speed is reduced, or this developing solution is carried into the fixing solution of the next step to lower the fixing speed,
This has caused new problems such as the fact that the developer reacts during long-term storage of the developer and loses its function and effect.

[0004]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, an object of the present invention is to provide a developing solution which does not cause silver stains even with rapid processing, has little desensitization, and does not impair fixability. An object of the present invention is to provide a developer composition for a black-and-white silver halide photographic light-sensitive material which does not lose its function and effect even when stored for a long time.

[0005]

The above objects of the present invention can be attained by the following developer composition for a black-and-white silver halide photographic light-sensitive material.

A black-and-white silver halide photograph containing at least one compound represented by the general formula [1] and at least one compound represented by the general formula [2] (Formula 2) A developer composition for a photosensitive material.

[0007] A black-and-white composition comprising at least one compound represented by the general formula [3] (formula 3) and at least one compound represented by the general formula [2] (formula 2) A developer composition for a silver halide photographic material.

A black-and-white silver halide photograph comprising at least one compound represented by the general formula [1] and at least one compound represented by the general formula [4] (Formula 4). A developer composition for a photosensitive material.

[0009] A black-and-white composition comprising at least one compound represented by the general formula [3] (Formula 3) and at least one compound represented by the general formula [4] (Formula 4) A developer composition for a silver halide photographic material.

Hereinafter, the present invention will be described specifically.

The general formula [1] will be described.

In the general formula [1], A ¹ is a hydroxy group, -SO ₃ M ¹ , -COOM ¹ (where M ¹ represents a hydrogen atom, an alkali metal atom or a substituted or unsubstituted ammonium ion), -N (R ³ ) ₂ groups (R ³ represents a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, which may be linked to each other to form a ring), and ALK has 2 to 12 carbon atoms. Represents a substituted or unsubstituted alkylene group, M ² is a hydrogen atom,

[0013]

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(R ⁴ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group having 10 or less carbon atoms, and X ⁻ represents a halide ion or a sulfonic acid. It represents an ion) or an -S-ALK-a ¹ group.

As the substituent, a halogen atom (for example,
Fluorine, chlorine, bromine), lower alkyl group (including those having a substituent, preferably those having 5 or less carbon atoms such as methyl group and ethyl group), lower alkoxy group (including those having a substituent; methoxy , Ethoxy, butoxy and the like having 5 or less carbon atoms), hydroxy group, sulfo group, lower allyl group (including those having a substituent, preferably having 5 or less carbon atoms), amino group, and COM _One group, a carbamoyl group (as defined above for M ₁ ), a phenyl group, and the like.

Specific examples of the general formula [1] are shown below.

[0017]

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Next, the general formula [2] will be described.

In the general formula [2] used in the present invention, Z ₂₁ and Y ₂₁ each represent an unsaturated 5-membered or 6-membered ring (for example, benzene, pyrrole, imidazole, pyrazole, pyrimidine, Pyridamine, pyrimidine, etc.), Z and Y together contain three or more nitrogen atoms, and have at least one mercapto group as a substituent. It may have a substituent other than a mercapto group, such as a halogen atom (for example, fluorine, chlorine, bromine), a lower alkyl group (including those having a substituent; a methyl group, an ethyl group, etc.) And a lower alkoxy group (including those having a substituent; methoxy, ethoxy, butoxy and the like having 5 carbon atoms).
The following are preferred. ), Hydroxy, sulfo,
A lower allyl group (including those having a substituent, preferably those having 5 or less carbon atoms), an amino group, a COOM ₂₁ group, and M ₂₁ include a carbamoyl group and a phenyl group as defined above for M ₁ . Particularly, it preferably has a hydroxy group, a COOM ₂₁ group, an amino group, or a sulfo group. Further, compounds represented by the following general formulas [A] to [F] in the general formula [1] are particularly preferable.

[0020]

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[In the formula, R ₂₁ , R ₂₂ and R ₂₃ are a halogen atom, a lower alkyl group (including those having a substituent, preferably those having 5 or less carbon atoms such as a methyl group and an ethyl group); Lower alkoxy groups (including those having a substituent; those having 5 or less carbon atoms are preferable), hydroxy groups, sulfo groups, and lower allyl groups (including those having a substituent; those having 5 carbon atoms or less are preferable). ), Amino group, CO
An OM ₂₁ group (M ₂₁ has the same meaning as M ₁ ), a carbamoyl group and a phenyl group, at least one of which is a mercapto group. In particular, the substituent other than the mercapto group preferably has a hydroxy group, a COOM ₂₁ group, an amino group, or a sulfo group. ]

[0022]

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[In the formula, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each a halogen atom, a lower alkyl group (including those having a substituent, and those having 5 or less carbon atoms such as a methyl group and an ethyl group are preferable.) ), Lower alkoxy groups (including those having a substituent, preferably those having 5 or less carbon atoms), hydroxy groups, sulfo groups, lower allyl groups (including those having a substituent, those having 5 or less carbon atoms) Is preferred.), An amino group, CO
An OM ₂₁ group (M ₂₁ has the same meaning as M ₁ ), a carbamoyl group and a phenyl group, at least one of which is a mercapto group. In particular, the substituent other than the mercapto group preferably has a hydroxy group, a COOM ₂₁ group, an amino group, or a sulfo group. ]

[0024]

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[Wherein R ₂₁ and R ₂₂ represent a halogen atom, a lower alkyl group (including those having a substituent, a methyl group,
Those having 5 or less carbon atoms such as an ethyl group are preferred. ), Lower alkoxy groups (including those having a substituent, preferably those having 5 or less carbon atoms), hydroxy groups, sulfo groups, lower allyl groups (including those having a substituent, those having 5 or less carbon atoms) Preferred)), an amino group, a COOM ₂₁ group (M ₂₁ is as defined above for M ₁ ), a carbamoyl group, and a phenyl group;
At least one is a mercapto group. In particular, the substituent other than the mercapto group preferably has a hydroxy group, a COOM ₂₁ group, an amino group, or a sulfo group. ]

[0026]

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[Wherein, R ₂₁ and R ₂₂ represent a halogen atom, a lower alkyl group (including those having a substituent, a methyl group,
Those having 5 or less carbon atoms such as an ethyl group are preferred. ), Lower alkoxy groups (including those having a substituent, preferably those having 5 or less carbon atoms), hydroxy groups, sulfo groups, lower allyl groups (including those having a substituent, those having 5 or less carbon atoms) Preferred)), an amino group, a COOM ₂₁ group (M ₂₁ is as defined above for M ₁ ), a carbamoyl group, and a phenyl group;
At least one is a mercapto group. In particular, the substituent other than the mercapto group preferably has a water-soluble group such as a hydroxy group, a COOM ₂₁ group, an amino group, or a sulfo group. ]

[0028]

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[In the formula, R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ are each a halogen atom, a lower alkyl group (including those having a substituent, and those having 5 or less carbon atoms such as a methyl group and an ethyl group are preferable.) ), Lower alkoxy groups (including those having a substituent, preferably those having 5 or less carbon atoms), hydroxy groups, sulfo groups, lower allyl groups (including those having a substituent, those having 5 or less carbon atoms) Is preferred.), An amino group, CO
An OM ₂₁ group (M ₂₁ has the same meaning as M ₁ ), a carbamoyl group and a phenyl group, at least one of which is a mercapto group. In particular, the substituent other than the mercapto group preferably has a hydroxy group, a COOM ₂₁ group, an amino group, or a sulfo group. ]

[0030]

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[Wherein R ₂₁ , R ₂₂ and R ₂₃ are each a hydrogen atom, a —SM ₂₁ group, a hydroxy group, a lower alkoxy group —C
OOM ₂₂ group, an amino group, -SO ₂₃ M ₂₃ group or a lower alkyl group, at least one of R _21, R _22, R ₂₃ represents an -SM ₂₁ group. M _21, M _22, M ₂₃ are each a hydrogen atom, an alkali metal atom or an ammonium group and may be the same or different. In the above general formula [F], the lower alkyl group and the lower alkoxy group represented by R ₂₁ , R ₂₂ and R ₂₃ are groups each having 1 to 5 carbon atoms, and they further have a substituent. And preferably a group having 1 to 3 carbon atoms, R ₂₁ ,
The amino group represented by R ₂₂ or R ₂₃ represents a substituted or unsubstituted amino group, and a preferred substituent is a lower alkyl group.

In the above formula [F], the ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

[0033]

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[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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Among the compounds represented by the general formula [3], preferred ones can be represented by the general formulas [3-a] and [3-b].

[0040]

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[In the general formula [3-a], R ₃₁ and R ₃₃ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted, an alkenyl group, an aralkyl group, a cycloalkyl group,
Optionally substituted phenyl, 5- or 6-membered containing 1 to 3 nitrogen atoms or 1 oxygen atom or 1 sulfur atom
R ₃₂ represents a direct bond or may be an substituted alkylene group, an alkylidene group, a phenylene group, an aralkylene group or —CONH
CH ₂ - represents, A ₃₃ is -COOM or -SO ₃ M (M
Is the same as M ¹ in the general formula [1]), and m ₃₃ is 1 or 2
It is. [In the general formula [3-b], R ₃₄ and R ₃₅ represent a hydrogen atom or a methyl group. M is preferably a hydrogen cation or an alkali metal ion (such as Na ⁺ or K ⁺ ).

Among the compounds represented by the general formula [3-a], those having the general formula [3-a-1] are more preferable. ]

[0043]

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[In the general formula [3-a-1], R ₃₆ and R ₃₇ represent a hydrogen atom or an alkyl group which may be substituted (for example, -CH
_{3, -C 2 H 5, -CH} 2 OH, etc. -CH ₂ COOH),
Cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.) and optionally substituted phenyl group (eg, phenyl group, tolyl group, p-chlorophenyl group, aminophenyl group, p-sulfophenyl group, p-sulfonamidophenyl group, etc.) 1-3 nitrogen atoms, or an oxygen atom 1 or 5-membered containing one sulfur atom, or 6-membered heterocyclic ring (e.g., furyl group, thienyl group), or represents a carboxylic acid group, R _36, R ₃₇ may be the same or different. l is 1,
2, 3 or 4. Specific examples of the compound represented by the general formula [3] are shown below.

[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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Among the compounds represented by the general formula [4], a compound selected from the following general formulas [4-a] and [4-b] is preferable.

[0051]

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In the general formulas [4-a] and [4-b], R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ each represent a hydrogen atom, -SM
₄₁ groups, hydroxy group, lower alkoxy group -COOM
₄₂ group, an amino group, an -SO ₃ M ₄₃ group or a lower alkyl group, at least one of _{R 41, R 42, R 43} , R 44 represents an -SM ₄₁ group. M ₄₁ , M ₄₂ and M ₄₃ each represent a hydrogen atom, an alkali metal atom or an ammonium group, and may be the same or different.

The above general formula [4-a] and general formula [4-a]
b), the lower alkyl group and the lower alkoxy group represented by R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ each have 1 carbon atom.
A group having from 5 to 5, which may further have a substituent, preferably a group having from 1 to 3 carbon atoms, represented by R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ The amino group represents a substituted or unsubstituted amino group, and a preferred substituent is a lower alkyl group.

The above general formula [4-a] and general formula [4-a]
In b), the ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

The general formula [4-a] and the general formula [4-a]
Specific examples of the compound represented by b) are shown below, but the present invention is not limited thereto.

[0056]

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[0057]

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[0058] Each amount of the general formula [1] to a compound of [4] of the present invention preferably has a developer is 10 ^-6 to 10 ^-1 mole per 1l, even ^{10-5 -} Particularly preferred is ² moles.

The compound of the present invention is a known compound,
It can be easily obtained.

The compound of the present invention has a function of trapping dissolved silver to prevent the generation of silver stain on the light-sensitive material, maintains the effect of preventing the silver stain of the developing solution, and exhibits an excellent long-term storage property. Therefore, rapid development processing can be performed, and a decrease in fixing speed can be prevented.

The developing agents which can be used in the present invention include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone 2,5-dimethylhydroquinone, 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-virazolidone, 1-phenyl-5-methyl -
3-pyrazolidone, etc.), aminophenols (for example,
o-aminophenol, p-aminophenol, N-methyl-o
-Aminophenol, N-methyl-p-aminophenol, 2,
4-diaminophenol, etc.), pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (eg, 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-amino Pyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-aminopyrazoline and the like can be used alone or in combination. Is preferably used in combination with 3-pyrazolidones and dihydroxybenzenes, or in combination with aminophenols and dihydroxybenzenes. The developing agent is preferably used usually in an amount of 0.01 to 1.4 mol / l.

In the present invention, examples of the sulfite and metabisulfite used as a preservative include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably at least 0.25 mol / l. Particularly preferably, it is at least 0.4 mol / l.

In the developing solution, if necessary, an alkali agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (eg, carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanol) Amines), dissolution aids (eg, polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers (eg, nonionic surfactants including polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, Antifoaming agents, antifoggants (for example, silver 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, nitrilo Acetates, such as polyphosphates), development accelerators (e.g. U.S. Pat. No. 2,304,025, JP-B-47-
No. 45541, etc.), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent can be added. The pH of the developer is preferably adjusted to 9.5 to 12.0.

The compound of the present invention is used as a special type of development processing by using an activator processing solution in which a developing agent is contained in a light-sensitive material, for example, an emulsion layer, and the light-sensitive material is processed in an alkaline aqueous solution to perform development. Is also good. Such a development process is often used as one of the methods for rapid processing of a photosensitive material in combination with a silver salt stabilization process using 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 large.

As the fixing solution, those having a commonly used composition can be used. The fixing solution is generally an aqueous solution comprising a fixing agent and others, and the pH is usually from 3.8 to 5.8. Sodium thiosulfate, potassium thiosulfate,
Use of thiosulfates such as ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate, and organic sulfur compounds capable of forming soluble stable silver complex salts, which are known as fixing agents Can be.

A water-soluble aluminum salt acting as a hardener, for example, aluminum chloride, aluminum sulfate, potassium alum and the like can be added to the fixing solution.

The fixing solution may optionally contain a preservative (for example, sulfite or bisulfite), a pH buffer (for example, acetic acid), a pH adjuster (for example, sulfuric acid), a chelating agent having a water softening ability. And the like.

The developer may be a mixture of fixed components, an organic aqueous solution containing glycol or amine, or a viscous liquid in a semi-kneaded state having a high viscosity. Further, it may be used after being diluted at the time of use, or may be used as it is.

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

The black-and-white silver halide photographic light-sensitive material according to the present invention is preferably processed using an automatic processor.
At this time, the processing is performed while replenishing a fixed amount of a developing solution proportional to the area of the photosensitive material. The amount of replenishment for development is 250 ml or less per m ² in order to reduce the amount of waste liquid. It is preferably at least 75 ml and at most 200 ml per m ² . 1m ² per 75ml
If the replenishing amount of the developing solution is less than the above range, satisfactory photographic performance cannot be obtained due to desensitization and softening.

According to the present invention, the total processing time (Dry to Dry) from the insertion of the leading end of the film to the automatic developing machine until it comes out of the drying zone when processing is performed using the automatic developing machine due to the demand for shortening the developing time. It is preferably 20 to 60 seconds. The term "total processing time" as used herein includes the total processing time required for processing a black-and-white silver halide photographic light-sensitive material. Time including all the time of process such as Dr
It is y to Dry time. If the total processing time is less than 20 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dry) is 30 to 60 seconds.

The silver halide emulsion used in the present invention (hereinafter referred to as silver halide emulsion or simply referred to as emulsion, etc.) includes, for example, silver bromide, silver iodobromide, silver iodochloride, chloroodor. Any silver halide, silver chloride, and other commonly used silver halide emulsions can be used, but silver chlorobromide or silver chloride containing 50 mol% or more of silver chloride is preferred.

(Standard deviation of particle size) / (Average value of particle size)
Monodisperse particles having a coefficient of variation of 15% or less represented by × 100 are preferred. The average particle size is preferably from 0.1 to 0.4 μm.

The effect of the present invention is remarkable in the processing of a light-sensitive material containing a hydrazine derivative as described in JP-A-56-106244 as a high contrast agent.
No. 841 pp. 540 (2) to 551 (13) hydrazine derivatives represented by general formula (I) or (II) and JP-A-4-98239 607
It is preferably used in a method for processing a light-sensitive material containing a nucleation accelerator described in pages (7) to 626 (26) in a constituent layer.

Various techniques and additives known in the art can be used for the silver halide emulsion of the present invention.

For example, in the silver halide photographic emulsion and the backing layer used in the present invention, various chemical sensitizers, color toning agents, hardeners, surfactants, thickeners, plasticizers, sliding agents,
A development inhibitor, an ultraviolet absorber, an antiirradiation dye, a heavy metal, a matting agent and the like can be further contained by various methods. The silver halide photographic emulsion and the backing layer of the present invention may contain a polymer latex.

These additives are described in more detail in Research Disclosure, Vol. 176, Item / 7643 (December, 1978) and 187, Item / 8716 (November, 1979). These are summarized below.

Additive Type RD / 7643 RD / 8716 Chemical sensitizer page 23 648 right column 2. Sensitivity increasing agent Same as above 3. 3. Spectral sensitizers, pages 23 to 24, right column, page 648 to supersensitizers, right column, page 649. Brightener page 24 5. 5. Antifoggant and stabilizer page 24 to 25 page 649, right column 6. Light absorbers, filter dyes, pages 25 to 26, right column, page 649 to ultraviolet absorbers, left column, page 650 7. Stain inhibitor 25 pages right column 650 pages left to right column 8. Dye image stabilizer page 25 Hardening agent Page 26 651 Left column 10. Binder page 26 Same as above 11. Plasticizers and lubricants Page 27 Right column on page 650 12. Coating aids, surfactants 26-27 Same as above 13. Examples of the support that can be used in the silver halide photographic light-sensitive material of the present invention include cellulose acetate, cellulose nitrate, and the like.
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 base treatment as required.

[0079]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 8 W / (m ² ···
After performing corona discharge with energy of (min), an antistatic liquid having the following composition was applied at a speed of 30 m / min using a roll-fit coating pan and an air knife so as to have the following amount.

(Preparation of Support Having Conductive Layer) After corona discharge into a 100 μm-thick polyethylene terephthalate subjected to a subbing treatment, an antistatic solution having the following composition was applied at 70 m / min so that the following amount was applied. The coating was performed at a speed using a roll-fit coating pan and an air knife.

Water-soluble conductive polymer P-6 0.6 g / m ² Hydrophobic polymer particle L-1 0.4 g / m ² Polyethylene oxide compound Ao-1 0.06 g / m ² Hardener E-8 0.2 g / m ² This was dried at 90 ° C. for 2 minutes and heat-treated at 140 ° C. for 90 seconds. This conductive layer was prepared by applying it on one side of a support.

[0083]

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(Preparation of Silver Halide Emulsion) A silver chloroiodobromide (70 mol% of silver chloride, 0.5 mol% of silver iodide and silver bromide other than silver chloride) emulsion was prepared by a double jet method.

During the mixing step from the formation of 5% of the final attained average particle size to the final attained average particle size, potassium hexabromorhodate is added to 8 × per mole of silver.
10 ⁻⁸ mol was added.

The resulting emulsion was desalted by a conventional flocculation method using a modified gelatin treated with phenyl isocyanate, and then dispersed in gelatin. The following emulsions [A] and [B] And [C] were added, and the average particle size was 0.1.
An emulsion comprising 30 μm cubic monodisperse grains (coefficient of variation 10%) was obtained.

[0087]

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The emulsion was added with citric acid and sodium chloride and
After adding 1-phenyl-5-mercaptotetrazole, adding chloroauric acid and sodium thiosulfate and chemically ripening at 60 ° C to reach the highest sensitivity, then 4-hydroxy-6-methyl-1,3,3
After ripening was stopped by adding 1 g of a, 7-tetrazaindene per mol of silver, 600 mg of potassium bromide and 150 mg of a sensitizing dye having the following structure SD-1 were added per 1 mol of silver halide.

(Preparation of Emulsion Coating Solution) 0.4 g of hydrazine derivative H-1, 1.5 g of nucleation accelerator H-2, 2 g of hydroquinone, and polymer latex P1 having the following structure were added to 1 mol of silver emulsion. 15 g, 450 m of inhibitor ST-1
g, 2 g of styrene-maleic acid polymer, 1 g of 1N sodium hydroxide solution, 1.5 g of the following structure S-1, S-3 as a coating aid, and 2,4-dichloro-6-hydroxy-1 as a hardener. ,
The sodium salt of 3,5-triazine was added.

(Preparation of Coating Solution for Emulsion Protective Layer) 1 mg of an aqueous solution containing 1.1 g of gelatin, 1 mg of formalin adduct of sodium bisulfite, 5.5 mg of 1-phenyl-4-hydroxymethyl-3-pyrazolidone were added per 1 m ² . 15 mg each of monodisperse silica having an average particle size of 3 μm and an average particle size of 8 μm was added with the following structure S-2 and citric acid as coating aids, and formalin was further added as a hardening agent. Further, a fluorine-based surfactant FA-33 was added so that the coating amount was 3 × 10 ⁻⁶ mol / m ² .

(Preparation of Backing Layer Coating Solution) To an aqueous solution containing 2.3 g of gelatin per 1 m ² , 100 mg of the water-soluble dye compound III-1, 25 mg of III-3, and 100 m3 of III-3 were added.
g, 350 mg of polymer latex P-1, 60 mg of styrene-maleic acid polymer, 150 mg of colloidal silica,
A mixture of [A], [B] and [C], sodium dodecylbenzenesulfonate as a coating aid, 55 g of glyoxal and E-2 as a hardener were added and stirred.

[0092]

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[0093]

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[0094]

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(Preparation of Backing Layer Protective Layer Coating Solution)
per m ^2, in an aqueous solution containing gelatin 0.7 g, the S-2 7m
g, a dispersion of monodispersed polymethyl methacrylate having an average particle size of 5.5 μm, a mixture of [A], [B], and [C], and a styrene-maleic acid polymer, followed by stirring, and glyoxal as a hardener. And 2,4-dichloro-6-hydroxy-1,3,
The sodium salt of 5-triazine was added.

(Preparation of Sample) On one side of a polyethylene terephthalate film support having the above antistatic layer, 15
After corona discharge at an energy of W / (m ² · min), the backing layer coating solution and the backing layer protective film layer coating solution prepared as described above were applied to the side having the antistatic layer. Further, one side of the support was subjected to corona discharge at an energy of 15 W / (m ² · min), and then an emulsion layer and an emulsion protective film layer were coated. The emulsion layer was coated and dried so that the silver amount was 3.5 mg / m ² and the gelatin amount was 1.7 mg / m ² .

[0097] and then developed with the following conditions with a developing solution and using a fixer plate making automatic developing machine G R · 26SR (produced by Konica) below.

<Processing Conditions> [Formulation of Developer] Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 25 g Potassium sulfite (55% W / V aqueous solution) 114 ml Potassium carbonate 55 g Hydroquinone 20 g 5-methylbenzotriazole 300 mg General formula [1] ] And a compound of the general formula [2] or a comparative compound (shown in Table 1) Potassium hydroxide Amount for adjusting the pH of the working solution to 10.5 Potassium bromide 3.3 g 1-Phenyl-3-pyrazolidone 750 mg Dissolve these in pure water And finished to 1 liter.

[Composition of Fixing Solution] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 ml Sodium sulfite 9.5 g Sodium acetate trihydrate 28 g Boric acid 6.7 g Sodium citrate dihydrate 2 g Acetic acid (90% W (W / W aqueous solution) Amount to adjust pH of used solution to 4.7 (Composition B) Pure water 17 ml Sulfuric acid (50% W / W aqueous solution) 2.5 g Aluminum sulfate (Al ₂ O ₃ equivalent content: 8.1% W / W aqueous solution) 21 g Fixation When the solution was used, the composition A and the composition B were dissolved in 500 ml of water in this order, and the solution was finished to 1 liter.

[Development Processing Conditions] Step Temperature Time Developing 38 ° C. 12 seconds Fixing 35 ° C. 10 seconds Rinse at room temperature 10 seconds Drying 50 ° C. 13 seconds Total 45 seconds Each process time includes the so-called wading transfer time to the next process.

[0102] replenisher using the same as the composition of the developer and fixer, the samples were 30 m ² performed while replenishing at the rate of developing 160 cc / m ² fixing 190 cc / m ^2. In order to examine the presence or absence of silver stain after the treatment, a 3.5 × 12 cm film piece was treated without exposure, and the stain on the film surface was visually observed. The development stain was evaluated on a five-point scale, with the worst stain being ranked 1 and the clean one being ranked 5. If the rank is less than 3, the state is not practically acceptable.

Developing speed: Relative sensitivity at the time of developing under the above conditions after exposure with He-Ne laser for ^10-6 seconds.

Fixing speed: The time (seconds) required for the photosensitive material sample to become transparent with the fixing solution after processing 30 m ² was measured and expressed as a relative speed.

Storage property: The prepared developer was packed in a polyethylene packaging material and heated at 60 ° C. for 20 days. After heat treatment,
A silver stain test was performed and a five-step table was performed. The worst dirt was given a rank of 1, and the clean one was given a rank of 5. The closer to rank 5, the more the effect of preventing silver contamination is not lost even when the developer is heated. If the rank is less than 3, the state is not practically acceptable.

Table 1 shows the results.

[0106]

[Table 1]

Example 2 The procedure of Example 1 was repeated except that the developer was changed to the following developer composition 2. Table 2 shows the results.

[Developer Composition 2] Diethylenetriaminepentaacetic acid pentasodium salt 1.5 g Diethylene glycol 25.0 g Sodium sulfite 50.0 g Potassium carbonate 55.0 g Hydroquinone 20.0 g 5-methylbenzotriazole 0.3 g General formula [2] and general formula [ 3] Compound or comparative compound (shown in Table 2) Potassium bromide 5.0 g 4-methyl-4-hydroxymethyl-1 phenyl-3-pyrazolidone 1.0 g Water was added to make 1 liter, and the pH was adjusted with potassium hydroxide.
Adjusted to 10.4.

[0109]

[Table 2]

Example 3 A hydrazine derivative having a silver halide emulsion layer composition was prepared using H-3.
Example 1 was repeated except that 0.35 g per mol of silver, H-42.0 g of nucleation accelerator and developer composition 3 shown below were used as the developer. Table 3 shows the results.

[Developer Composition 3] Potassium sulfite 65.0 g Hydroquinone 15.0 g N-methyl-P-aminophenol 1/2 sulfate 0.5 g Ethylenediaminetetraacetic acid disodium salt 0.5 g Potassium carbonate 50.0 g Potassium bromide 5.0 g Benzotriazole 0.4 g Compounds of the general formulas [1] and [4] of the present invention or comparative compounds (shown in Table 3) Water was added to 1 liter, and the pH was adjusted with potassium hydroxide.
Adjusted to 10.4.

[0112]

[Table 3]

[0113]

Embedded image

Example 4 The procedure of Example 3 was repeated except that the developing solution was changed to the following developing solution composition 4. Table 2 shows the results.

[Developer Composition 4] Diethylenetriaminepentaacetic acid pentasodium salt 1.5 g Diethylene glycol 40.0 g Sodium sulfite 45.0 g Potassium carbonate 50.0 g Hydroquinone 20.0 g 5-Methylbenzotriazole 0.3 g 5-Nitroindazole 0.1 g Boric acid 5.0 g The present invention Compounds of the general formulas [3] and [4] or comparative compounds (shown in Table 4) Potassium bromide 5.0 g 4-Methyl-4-hydroxymethyl-1phenyl-3-pyrazolidone 1.0 g Water was added. 1 liter and the pH is adjusted with potassium hydroxide
Adjusted to 10.4.

[0116]

[Table 4]

[0117]

According to the present invention, black-and-white halogenation which does not cause silver stains even when processed rapidly, causes little desensitization, does not impair fixability, and does not lose its effect even when stored in a developer for a long period of time. A developer composition for a silver photographic light-sensitive material could be provided.

Claims (4)

(57) [Claims] 1. A black-and-white silver halide photographic material comprising at least one compound represented by the following general formula [1] and at least one compound represented by the following general formula [2]. Developer composition. General formula [1] A ¹ -ALK-SM ² [where A ¹ is a hydroxy group, -SO ₃ M ¹ , -COOM ¹ (where M
¹ represents a hydrogen atom, an alkali metal atom or a substituted or unsubstituted ammonium ion), -N (R ³ ) ₂ group (R ³ represents a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, and is linked to each other May form a ring), ALK
Represents a substituted or unsubstituted alkylene group having 2 to 12 carbon atoms, M ² represents a hydrogen atom, (R ⁴ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group having 10 or less carbon atoms, and X ⁻ represents a halide ion or a sulfonate ion. ) or an -S-ALK-a ¹ group. [Chemical formula 2] [In the formula, Z ₂₁ and Y ₂₁ are each a ring forming an unsaturated 5- or 6-membered ring, and Z ₂₁ and Y ₂₁ together contain three or more nitrogen atoms, and at least one It has a mercapto group as a substituent. ] 2. A black-and-white silver halide photographic material comprising at least one compound represented by the following general formula [3] and at least one compound represented by the above general formula [2]. Developer composition. Embedded image Wherein A ₃₁ and A ₃₂ are each independently a resin group, an alicyclic group, an araliphatic group, an aromatic group or a hetero- or 5-membered ring, and m ₃₁ and m ₃₂ are respectively 1, 2 and 3; n ₃₁ is 1 or 2; B ₃₁ and B ₃₂ are each independently of the formulas —COOM ′ ₃₁ , —SO ₃ M ′ ₃₁ , and —CON (X
_{31) (Y 31), -} S-Z '31 and _{-SO 2 N (X 31) (} Y 31) (X 31 and Y ₃₁ each represents a hydrogen atom or a hydroxyl group, optionally substituted by a carboxylic acid group or sulfonic acid group Good carbon number 1
8 is an alkyl group and an aryl group, M _'31 is a monovalent cation, Z' groups is ₃₁ has the same meaning as X ₃₁ and Y _31, which is represented by but not a hydrogen atom) It is. ] 3. A black-and-white silver halide photographic material comprising at least one compound represented by the general formula [1] and at least one compound represented by the following general formula [4]. Developer composition. Embedded image [In the formula, Z ₄₁ and Y ₄₁ are each a ring forming an unsaturated 5- or 6-membered ring, and Z ₄₁ and Y ₄₁ together contain three or more nitrogen atoms, and at least one It has a mercapto group as a substituent. ] 4. A black-and-white silver halide photographic material comprising at least one compound represented by the general formula [3] and at least one compound represented by the general formula [4]. Developer composition.