JPH10246937A - Developing composition for black-and-white silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a concentrated developing composition capable of processing in a low replenishing rate while maintaining superior photographic performance and rapid processing ability, by incorporating an ascorbic acid derivative and Na ions not below a specified concentration and not above a specified molar ratio Na/(Na+K). SOLUTION: This developing composition contains an ascorbic acid derivative and Na ions in a concentration of >=1.8mol/l and it has a Na/(Na+K) molar ratio of <=0.6, and if <1.8mol/l, low replenishing is impossible, and if the Na ions are increased to maximum, the optical density after development is probable to lower, and it is preferred to restrain them to <=3.5mol/l. The developing composition is concentrated to a concentration degree Rd of >=1.5 times, where Rd =(Vc +Vw )/Vc in order to give preferable performance. In the formula, Vc (ml) is solution amount of the concentrated developer; Vw (ml) is added water necessary for usable solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a developing composition for a black-and-white silver halide photographic light-sensitive material, and more particularly to a highly concentrated developing composition for a black-and-white silver halide photographic light-sensitive material which is effective in reducing the replenishment amount.

[0002]

2. Description of the Related Art A black-and-white silver halide photographic light-sensitive material for printing plate making and the like is generally an automatic developing machine having a developing section, a fixing section, a washing section or a stabilizing section and a drying section after exposure. Processed while replenishing the replenisher. 2. Description of the Related Art In recent years, there has been a demand for reduction of photographic waste liquid due to increasing interest in the environment, and one of the means is to reduce the replenishment amount of a processing liquid.

In recent years, attention has been focused on improving the working environment, particularly on shortening working hours. In the printing and plate making industry, there is an increasing demand for a reduction in working time. Therefore, conventionally, the entire processing time from development to drying of a photosensitive material (Dry
(Dry to Dry) of 90 seconds or more has been strongly desired to be further reduced.

[0004] Developers are often supplied in concentrated form for convenience in saving storage space and for transport. These concentrates are diluted with water to a proper concentration at the time of use. The higher the concentration of the concentrated solution, the smaller the number of dilutions required to obtain a predetermined amount of liquid and the smaller the storage space, so that it is required to increase the concentration of the developing concentrated solution.

[0005]

However, in the conventional developer formulation for low replenishment, if the concentration is increased to more than 1.5 times, the precipitation at low temperature is deteriorated. So 200m
The photographic performance (sensitivity, halftone dot fluctuation, etc.) can be satisfied even when processed with a replenishment amount of 1 / m ² or less, and there is no defective fixation even after rapid processing, and it is possible to concentrate more than 1.5 times. Development concentrates have been desired.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a developing concentrated solution capable of performing low replenishment processing while satisfying photographic performance and rapid processing performance.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to contain ascorbic acids and 1.8 mol / l or more of Na ions, to reduce the amount of sodium ions to Na (mol / l) and the amount of potassium ions to This is achieved by a developing composition for a black-and-white silver halide photographic material having a sodium ratio Nr defined by Nr = Na / (Na + K) as K (mol / l) of 0.6 or less.

That is, the present inventors have focused on potassium and sodium present in a developing solution, and have found that it is possible to secure fixability in a concentrated and low-replenishment system, thereby leading to the present invention. .

Hereinafter, the present invention will be described in detail for each item.

<< Developing Composition >> The developing composition of the present invention (hereinafter also referred to as “developed concentrate”) is prepared by adding the amount V _{c of the} developed concentrated solution.
(Ml), the amount of water _Vw (m
As _{l), R d = (V} c + V w) / V c represented by enrichment R _d 1.5 times or more, even 1.6 times or more, and very still more 1.8 times or more It is concentrated and has favorable performance.

The concentrated developing solution contains various ions in the form of a metal salt of a material contained in the developing solution. Sodium ions and potassium ions are usually used as metal ions from the viewpoint of availability and cost. These are often added as preservatives, chelating agents, buffers and pH adjusters. Also, sodium ions and potassium ions can be used as a developing agent, an inhibitor and the like.

In the present invention, the amount of sodium ions is at least 1.8 mol per liter of the concentrated developing solution, and the sodium ratio as defined above is at most 0.6. When the amount of sodium ions is less than 1.8 mol / l, low replenishment cannot be performed.
Further, when the amount of sodium ions is increased to the maximum width, the optical density after development may be reduced.
Mol / l or less. More preferably, it is from 1.8 mol / l to 2.6 mol / l. Further, when the sodium ratio exceeds 0.6, the performance fluctuation becomes large at low replenishment. Also, the suitability for rapid processing is reduced. The sodium ratio is preferably at least 0.2, more preferably at least 0.1.
It is 35 or more and 0.6 or less.

The developing concentrate of the present invention contains ascorbic acid or a derivative thereof as a developing agent. As ascorbic acid or a derivative thereof, a compound selected from the following formulas (A) and (Aa) is preferably used.

[0014]

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In the formula, R ₁ and R ₂ each represent an alkyl group, an amino group, an alkoxy group or an alkylthio group, which may have a substituent, and R ₁ and R ₂ are bonded to each other to form a ring. May be formed. k represents 0 or 1, and when k = 1, X represents -CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

In the compound represented by the general formula (A), a compound represented by the following general formula (Aa) in which R ₁ and R ₂ are bonded to each other to form a ring is preferred.

[0017]

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In the formula, R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an amino group, an alkoxy group, or a sulfo group, a carboxyl group, an amide group, or a sulfonamide group, and Y ₁ represents O or S is represented, and Y ₂ represents O, S or NR ₄ . R ₄ represents a substituted or unsubstituted alkyl group or aryl group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

The alkyl group in the general formula (A) or the general formula (Aa) is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group or an unsubstituted amino group. An amino group substituted with a lower alkyl group is preferable, an alkoxy group is preferably a lower alkoxy group, and an aryl group is preferably a phenyl group or a naphthyl group, and these groups may have a substituent. Examples of the substitutable group include a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, and a sulfonamide group.

Specific examples of the compound represented by formula (A) or (Aa) are shown below, but the invention is not limited thereto.

[0021]

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[0022]

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These compounds are typically ascorbic acid or erythorbic acid and salts thereof or derivatives derived therefrom, and are commercially available or can be easily synthesized by known synthesis methods.

In combination with the above ascorbic acid or erythorbic acid developing agents, 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.) and aminophenols (eg, o-aminophenol, p-aminophenol, N
Auxiliary developing agents such as -methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol and the like and dihydroxybenzenes (e.g., hydroquinone, methylhydroquinone, chlorohydroquinone, hydroquinone monosulfonate). It is preferred to use. In this case, the developing agents such as 3-pyrazolidones and aminophenols are used in an amount of 0.0
It is preferably used in an amount of from 01 to 1.4 mol. The amount of ascorbic acid or erythorbic acid used is about 0.05 to 1 mol per liter of developer used.

In the present invention, in order to carry out rapid processing with a lower developing replenishing amount, the following general formula (S)
It is preferable to add a compound represented by the following formula.

Formula (S) Z ₁ -SM _{3 In the} formula, Z ₁ is an alkyl group, an aromatic group or a heterocyclic group, and is a hydroxyl group, a —SO ₃ M ₄ group, a —COOM.
_At least one selected from the group consisting of ₄ groups (where M ₄ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, or a substituted or unsubstituted ammonium group Or substituted by at least one substituent selected from this group. M ₃ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted amidino group (which may form a hydrohalide or a sulfonate).

In the general formula (S), the alkyl group represented by Z ₁ preferably has 1 to 30 carbon atoms, particularly a straight-chain, branched or cyclic alkyl group having 2 to 20 carbon atoms. It may be a group and may have a substituent in addition to the above substituents. The aromatic group represented by Z ₁ preferably has 6 carbon atoms.
To 32 monocyclic or condensed rings, which may have a substituent in addition to the above substituents. The heterocyclic group represented by Z ₁ is preferably a monocyclic or condensed ring having 1 to 32 carbon atoms, and contains 1 to 6 heteroatoms in one ring independently selected from nitrogen, oxygen and sulfur. And may have a substituent in addition to the above. Of the compounds represented by the general formula (S), preferably, Z ₁ is 2
The compound is a heterocyclic group having at least two nitrogen atoms.

The ammonium group preferably has 2 carbon atoms.
0 or less and the substituent is a substituted or unsubstituted straight chain,
It has a branched or cyclic alkyl group (methyl group, ethyl group, benzyl group, ethoxypropyl group, cyclohexyl group, etc.), substituted or unsubstituted phenyl group, and naphthyl group.

Further, among the compounds represented by the general formula (S), more preferred are the compounds represented by the following general formula (Sa).

[0030]

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In the formula, Z represents an unsaturated 5-membered or 6-membered heterocyclic ring having a nitrogen atom (pyrrole ring, imidazole ring, pyrazole ring, pyrimidine ring, pyridazine ring, pyrazine ring, etc.). a required group, a compound having at least one -SM ₃ or thione group and a hydroxyl _{group, -COOM 3, -SO 3 M 3} ,
It has at least one substituent selected from the group consisting of a substituted or unsubstituted amino group and a substituted or unsubstituted ammonium group. In the formula, R ¹¹ and R ¹² represent a hydrogen atom, -S
M ₃ groups, halogen atoms, alkyl groups (including those having a substituent), alkoxy groups (including those having a substituent), hydroxyl groups, —COOM ₃ , —SO ₃ M ₃ , alkenyl groups (substituents include those with), amino group (including those having a substituent) include those having a carbamoyl group (substituent), a phenyl group (including those having a substituent), with R ¹¹ and R ¹² A ring may be formed. The ring that can be formed is a 5- or 6-membered ring,
Preferred is a nitrogen-containing heterocycle. M ₃ is the same as M ₃ defined for the compound represented by formula (S). Preferably Z is a group forming a heterocyclic compound containing two or more nitrogen atoms may have a substituent other than the -SM ₃ or thione group, as the substituent, a halogen atom ( For example, fluorine, chlorine, bromine, 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; methoxy,
Those having 5 or less carbon atoms such as ethoxy and butoxy are preferred. ), A lower alkenyl group (including those having a substituent, preferably having 5 or less carbon atoms), a carbamoyl group, a phenyl group and the like. Furthermore, the general formula (Sa)
In the above, compounds represented by the following general formulas A to F are particularly preferred.

[0032]

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In the formula, R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ each represent a hydrogen atom, —SM ₃ , a halogen atom, a lower alkyl group (including those having a substituent, and a carbon atom such as a methyl group or an ethyl group). 5 or less is preferred.), including those with lower alkoxy group (substituent. those having 5 or less carbon atoms is preferred.), hydroxy group, -COOM _4, -SO ₃ M _5, a lower alkenyl group ( Including those having a substituent, having 5 carbon atoms
The following are preferred. ), An amino group, a carbamoyl group and a phenyl group, at least one of which is —SM ₃ . M ₃ , M ₄ and M ₅ each represent a hydrogen atom, an alkali metal atom or an ammonium group, and may be the same or different. In particular, -SM ₃ except as the substituent a hydroxy _{group, -COOM 3, -SO 3 M 3} , preferably has a water-soluble group such as an amino group. The amino group represented by R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ represents a substituted or unsubstituted amino group, and a preferable substituent is a lower alkyl group. The ammonium group is a substituted or unsubstituted ammonium group,
Preferably it is an unsubstituted ammonium group.

Specific examples of the compound represented by formula (S) are shown below, but it should not be construed that the invention is limited thereto.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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The compound represented by the formula (S) is preferably used in an amount of 10 ^-6 to 10 ^-1 mol, more preferably 10 ^-5 to 10 ^-2 mol, per liter of the developer used. .

Examples of the sulfite and metabisulfite used as a preservative include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite.
In the developer used, the sulfite is used in an amount of 0.05 mol / l or more, preferably 0.1 mol / l or more.

An alkali agent (eg, sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (eg, carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.) are added to the developer. Preferably. Carbonates are preferred as pH buffers. 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 salts, nitrilotriacetates, polyphosphates, etc.), development accelerators (eg, US Pat. No. 2,304) , No. 25, and Japanese Patent Publication No. 47-45541), a hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof), or an antifoaming agent. PH of developer used is 8.5 or more and 11
It is preferable that the pH be adjusted to less than 9.0.
It is less than 10.7.

<< Photosensitive Material >> The photosensitive material treated with a developer using the developing composition of the present invention preferably contains a quaternary onium compound and / or a hydrazine derivative.

The quaternary onium compound is a compound having a quaternary cation group of a nitrogen atom or a phosphorus atom in the molecule, and is preferably a compound represented by the general formula (P).

[0046]

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In the formula, Q represents a nitrogen atom or a phosphorus atom;
₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom or a substituent, and X ⁻ represents an anion. R _{5 to} R ₈ may be linked to each other to form a ring.

As the substituent represented by R _{5 to} R ₈ , an alkyl group (methyl group, ethyl group, propyl group, butyl group,
Hexyl group, cyclohexyl group, etc., alkenyl group (allyl group, butenyl group, etc.), alkynyl group (propargyl group, butynyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), heterocyclic group (piperidinyl group, piperazinyl group) , Morpholinyl group, pyridyl group, furyl group, thienyl group, tetrahydrofuryl group, tetrahydrothienyl group,
Sulfolanyl group), an amino group and the like.

The ring which may be formed by linking R _{5 to} R ₈ includes a piperidine ring, a morpholine ring, a piperazine ring,
Examples include a quinuclidine ring, a pyridine ring, a pyrrole ring, an imidazole ring, a triazole ring, and a tetrazole ring.

The groups represented by R _{5 to} R ₈ are a hydroxyl group,
It may have a substituent such as an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, an alkyl group and an aryl group.

As R ₅ , R ₆ , R ₇ and R ₈ , a hydrogen atom and an alkyl group are preferred.

Examples of the anion represented by X ⁻ include inorganic and organic anions such as a halogen ion, a sulfate ion, a nitrate ion, an acetate ion and a p-toluenesulfonic acid ion.

More preferably, the following general formulas (Pa) and (P
b) or a compound represented by (Pc); and a compound represented by the following general formula [T].

[0054]

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In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a group of nonmetal atoms for completing a nitrogen-containing heterocyclic ring, and may contain an oxygen atom, a nitrogen atom and a sulfur atom. And the benzene ring may be condensed. A ¹ , A ² , A ³ , A ⁴ and A ⁵
May have a substituent and may be the same or different. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxyl group, an alkoxy group, and an aryloxy group. Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group. Preferred examples of A ¹ , A ² , A ³ , A ⁴ and A ⁵ include a 5- to 6-membered ring (pyridine,
Imidazole, thiozole, oxazole, pyrazine,
Each ring such as pyrimidine), and a more preferred example is a pyridine ring.

_BP represents a divalent linking group, and m represents 0 or 1.
Represents Examples of the divalent linking group include an alkylene group, an arylene group, an alkenylene group, —SO ₂ —, —SO—, and —O
—, —S—, —CO—, and —N (R ⁶ ) — (R ⁶ represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Preferred examples of B _p include an alkylene group and an alkenylene group.

R ¹ , R ² and R ⁵ each have 1 to 20 carbon atoms
Represents an alkyl group. R ¹ and R ² may be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group, and the substituent is the same as the substituents described as the substituents for A ¹ , A ² , A ³ , A ⁴ and A ⁵ .

Preferred examples of R ¹ , R ² and R ⁵ include:
Each is an alkyl group having 4 to 10 carbon atoms. More preferred examples include a substituted or unsubstituted aryl-substituted alkyl group.

[0059] X _p ^- is a counter ion necessary to refer balancing the charge of the whole molecule, expressed as chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p- toluenesulfonate, the oxalato or the like. n _p represents the number of counter ions required to balance the charge of the whole molecule, and n _p is 0 in the case of an internal salt.

[0060]

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The substituent R ₉ of the phenyl group of the triphenyltetrazolium compound represented by the general formula [T],
R ₁₀ and R ₁₁ are preferably a hydrogen atom or a compound having a negative Hammett sigma value (σP) indicating the degree of electron withdrawing property.

The Hammett's sigma value for the phenyl group is described in many literatures, for example, Journal of Medical Chemistry.
Chemistry) 20, vol. 304, p. As a group having a particularly preferable negative sigma value, for example, a methyl group (σP = −0.17 or less, all of which can be seen in reports by C. Hansch et al.)
P value), ethyl group (-0.15), cyclopropyl group (-0.21), n-propyl group (-0.13), is
o-propyl group (-0.15), cyclobutyl group (-
0.15), n-butyl group (-0.16), iso-butyl group (-0.20), n-pentyl group (-0.1
5), cyclohexyl group (-0.22), amino group (-
0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.27),
Ethoxy group (-0.24), propoxy group (-0.2
5), butoxy group (-0.32), pentoxy group (-
0.34), etc., each of which has the general formula [T]
Is useful as a substituent of the compound of

N represents 1 or 2, and examples of the anion represented by X _T ^n- include halogen ions such as chloride ion, bromide ion and iodide ion, nitric acid, sulfuric acid, and the like.
Acid radicals of inorganic acids such as perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically p-
Lower alkylbenzene sulfonic acid anions such as toluene sulfonic acid anion; higher alkyl benzene sulfonic acid anions such as p-dodecyl benzene sulfonic acid anion; higher alkyl sulfate anions such as lauryl sulfate anion; boric acid anions such as tetraphenyl boron; Dialkyl sulfosuccinate anions such as 2-ethylhexyl sulfosuccinate anion,
Examples thereof include higher fatty acid anions such as cetyl polyethenoxy sulfate anion, and polymers having an acid radical attached to a polymer such as polyacrylate anion.

Hereinafter, specific examples of the quaternary onium compound will be shown below, but it should not be construed that the invention is limited thereto.

[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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The above quaternary onium compound can be easily synthesized according to a known method. For example, the above tetrazolium compound can be obtained from Chemical Reviews 55 p. 3
35-483 can be referred to.

The addition amount of these quaternary onium compounds is about 1 × 10 ^-8 to 1 mol, preferably 1 × 10 ^-7 to 1 × 10 ^-1 mol per mol of silver halide. These can be added to the light-sensitive material at any time from the time of silver halide grain formation to the time of coating.

The quaternary onium compound may be used alone or
More than one species may be used in combination. It may be added to any of the constituent layers of the light-sensitive material, but preferably at least one of the constituent layers on the side having the silver halide emulsion layer.
Layer and further added to the silver halide emulsion layer and / or the layer adjacent thereto.

The hydrazine derivative is preferably represented by the following general formula [H].

[0079]

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In the general formula [H], A ₀ is an aliphatic group,
An aliphatic group represented by A ₀ represents an aromatic group or a heterocyclic group, preferably has 1 to 30 carbon atoms, and is particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. . Specific examples include, for example, a methyl group, an ethyl group, a t-butyl group, an octyl group, a cyclohexyl group, a benzyl group and the like. These are further suitable substituents (for example, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group) , An arylthio group, a sulfoxy group, a sulfonamide group, a sulfamoyl group, an acylamino group, a ureido group, etc.).

The aromatic group represented by A ₀ is preferably a monocyclic or condensed-ring aryl group, for example, a benzene ring or a naphthalene ring. The heterocyclic group represented by A ₀ is preferably a monocyclic or condensed heterocyclic ring containing at least one hetero atom selected from nitrogen, sulfur, and oxygen atoms. Examples thereof include a pyrrolidine ring, an imidazole ring, a tetrahydrofuran ring, and morpholine. Ring, pyridine ring, pyrimidine ring, quinoline ring, thiazole ring, benzothiazole ring,
A thiophene ring, a furan ring and the like.

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 groups include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a substituted amino group, an acylamino group,
Sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfothio group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, alkyloxycarbonyl group, aryl Examples thereof include an oxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamide group, a sulfonamide group, a carboxy group, a phosphoric acid amide group, and the like. These groups may be further substituted.

Among these groups, the developer used is pH 1
0.7 or less, total processing time (Dry to Dry)
Is treated in 80 seconds or less, a substituent having an pKa of 7 to 11 having an acidic group is preferable, and specific examples thereof include a sulfonamide group, a hydroxyl group, and a mercapto group. Can be

A ₀ preferably contains at least one diffusion-resistant group or silver halide-adsorbing group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable, and the ballast group is a photographically inert group having 8 or more carbon atoms, for example, an alkyl group, an alkenyl group, an alkynyl group, Examples thereof include an alkoxy group, a phenyl group, a phenoxy group, and an alkylphenoxy group.

As the silver halide adsorbing group, thiourea,
Examples 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.

B ₀ represents a blocking group, preferably -G ₀ -D ₀ G ₀ represents a -CO- group, a -COCO- group,
CS-group, -C (= NG ₁ D ₁ ) -group, -SO- group, -S
Represents an O ₂ — group or a —P (O) (G ₁ D ₁ ) — group. G ₁ represents a simple bond, —O— group, —S— group, or —N (D ₁ ) — group. D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in a molecule, they may be the same or different.

D ₀ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group,
Represents an alkylthio group or an arylthio group.

Preferred G ₀ is -CO- group, -CO
Of the CO- groups, particularly preferred is a -COCO- group. Preferred D ₀ includes a hydrogen atom, an alkoxy group, an amino group and the like.

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

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

[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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When a hydrazine derivative is contained, a nucleation promoting agent represented by the following general formula [Na] or [Nb] or a nucleation accelerator represented by the above general formula (P) is used in order to effectively promote the contrast enhancement by the hydrazine derivative. It is preferable to use a quaternary onium compound.

[0097]

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In the general formula [Na], R ₁₂ , R ₁₃ , R
₁₄ 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. R ₁₂ , R ₁₃ and R ₁₄ 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 examples of the adsorptive group include a heterocyclic ring, a mercapto group, a thioether group, a thione group, and a thiourea group.

A preferred embodiment of the general formula [Na] is a compound represented by the following general formula [Na-a].

[0101]

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In the general formula [Na-a], R ⁷ , R ⁸ ,
R ⁹ and R ¹⁰ represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group,
Represents a substituted alkynyl group, an aryl group, a substituted aryl group, a saturated or unsaturated hetero ring. These can be linked to each other to form a ring. R ⁷ , R ⁸ and R ⁹ , R
Each set of ¹⁰ cannot be a hydrogen atom at the same time.

X represents an S, Se, or Te atom.

L ₁ and L ₂ represent a divalent linking group. Specific examples include combinations of the following groups and groups having appropriate substituents (for example, an alkylene group, an alkenylene group, an arylene group, an acylamino group, and a sulfonamide group).

-CH _2- , -CH = CH-, -C ₂ H
₄ -, _{pyridiyl, -N (Z 1) - (} Z 1 represents a hydrogen atom, an alkyl group or an aryl group), - O -, - S -, -
(CO) -, - (SO 2) -, - CH 2 N-, also preferably contains at least one or more of the following structure in the linking group.

-[CH ₂ CH ₂ O]-,-[C (CH ₃ )
_{HCH 2 O] -, - [} OC (CH 3) HCH 2 O] -, -
[OCH ₂ C (OH) HCH ₂ ] — Specific examples of the compound represented by the general formula [Na] are shown below.

[0107]

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[0108]

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[0109]

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In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic or heterocyclic group. R ₁₅ is a hydrogen atom,
It represents an alkyl group, an alkynyl group, or an aryl group, but Ar and R ₁₅ 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 examples of the compound represented by the general formula [Nb] include the following.

[0112]

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[0113]

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<Processing> In order to reduce the amount of waste liquid, it is preferable to perform processing while performing a certain amount of replenishment of development in proportion to the area of the photosensitive material. The amount of replenishment for development is preferably from 30 to 250 ml, more preferably from 30 to 250 ml, per m ² of the photosensitive material.
00 ml. The development replenisher may be the same as or different from the developer mother liquor in the tank of the automatic processor. The replenishment amount of the development referred to here is the replenishment amount of the solution when replenished with the same solution as the developing mother liquor, and is the total amount of the concentrated solution and the water when the replenishment solution is replenished with a solution diluted with water.

The temperatures of the developing solution, the fixing solution, the washing water and the stabilizing solution are preferably from 10 to 45 ° C., and the respective temperatures may be separately adjusted.

When processing using an automatic developing machine, the entire processing time (from dry to dry to development, fixing, bleaching, washing with water, and the like) from the insertion of the front end of the photosensitive material into the automatic developing machine to the discharge from the drying zone. The time including all steps such as stabilization and drying) is preferably from 10 to 80 seconds, and more preferably from 15 to 60 seconds, in order to meet the demand for shortening the processing time.
If the total processing time is less than 10 seconds, satisfactory photographic performance may not be obtained due to desensitization or softening. In order to stably process a large amount of photosensitive material of 100 m ² or more, the development time is preferably 2 to 22 seconds.

In order to cope with the rapid processing as described above, processing at a high temperature of 30 ° C. or higher has become common. However, in an automatic developing machine, the liquid level is usually in contact with air, and The amount of evaporation of the processing liquid increases. By the way, in recent years, electronic precision equipment such as scanners and imagesetters have become widespread, and automatic developing machines have been often installed near these equipment. It is harmful to, and sometimes causes failure. For this reason, an automatic developing machine is provided with an exhaust duct, and often sends exhaust air to the outside with a strong suction force. These exhaust ducts also increase the amount of water evaporation. In addition, when processing is carried out with a low replenishment, particularly when the developer is replenished at 200 ml or less per 1 m ² of the photosensitive material, the amount of the replenished liquid is reduced, so that the evaporation of water from the liquid surface remarkably occurs, and the running performance, particularly Problems such as fog, black spots and a decrease in the maximum density are likely to occur.

For this reason, in the present invention, it is preferable to carry out the treatment while replenishing water. The water replenishment referred to here is as described in JP-A-1-281446.
This is a method of replenishing water when supplying the replenisher. Water replenishment is preferably (1) supplying a fixed amount of water at the start of the development process, (2) replenishing water based on the elapsed time of the development process, and (3) replenishing water based on information from the liquid level sensor. (4) water replenishment based on information on the specific gravity of the processing solution, (5) water replenishment based on the area of the photosensitive material to be processed, (6) based on the suction force of the exhaust duct from the liquid level. Replenishing with water is mentioned, and these are employed alone or in combination.

[0119]

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 >> Aqueous solution of silver nitrate and NaCl
Silver chloride 7 by a simultaneous mixing method using a mixed aqueous solution of
At 0 mol%, silver halide grains consisting of silver bromide were grown. Mixing is at 50 ° C., pAg 7.8, pH 3.0.
During the grain formation, a water-soluble rhodium salt was added in an amount of 2 × 10 ⁻⁷ mol per mol of silver. Then, it is washed with desalinated water by flocculation method and the following compounds [A] and [B]
A fungicide comprising the mixture of [C] and ossein gelatin were added and redispersed. The EAg after redispersion was 220 mV. The resulting emulsion had an average particle size of 0.19 μm and a coefficient of variation (standard deviation divided by the average particle size and multiplied by 100).
It was an emulsion of 2% monodisperse cubic grains.

After adjusting the pH of the obtained emulsion with citric acid,
The pAg was adjusted with KBr, and 5 mg of chloroauric acid and 0.5 mg of sulfur were added per mole of silver, and the mixture was chemically ripened at 53 ° C. for 50 minutes. After ripening, 300 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added per mole of silver.

<< Preparation of a silver halide photographic light-sensitive material >> One of a 100 μm-thick polyethylene terephthalate film having a 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941) The following formulations (1) to (3) were simultaneously coated on the undercoat layer in the order close to the undercoat layer.
On the other subbing layer on the opposite side, a backing layer was coated according to the following formula (4) so that the amount of gelatin became 2.0 g / m ² , and further, the protection of the following formula (5) was further applied. The layer was applied so that the amount of gelatin became 1.0 g / m ² to obtain a sample.

Formulation of hydrophilic colloid layer (1) Gelatin 0.6 g / m ² Surfactant: Saponin 100 mg / m ² Dye D-1 17 mg / m ² Silver halide emulsion layer formulation (2) Gelatin 1.5 g / m ² halide emulsion silver amount 3.5 g / m ² sensitizing dye Sd-1 0.5 mg / m ² sensitizing dye Sd-2 0.5 mg / m ² hydrazine derivative: 3 × 10 ^-5 mol shown in Table 1 / M ² nucleation accelerator: Na-12 1 × 10 ⁻⁴ mol / m ² polymer latex l 0.5 g / m ² colloidal silica 0.25 g / m ² hydroquinone 50 mg / m ² water-soluble polymer V-1 20 mg / m ² surfactant: saponin 0.1 g / m ^2: sodium sulfosuccinic acid isopentyl -n- decyl ester 8 mg / m ² silver halide emulsion protective layer formulation (3) gelatin 0.9 g / m ² matting agent: mean particle 3.5μm polymethylmethacrylate beads 30 mg / m ² Surfactant: Sodium sulfosuccinic acid di (2-ethylhexyl) ester 10 mg / m ² Surfactant: F-1 0.6mg / m ² Hardener: HA-1 150 mg / m ² Backing layer formulation (4) Gelatin 2.0 mg / m ² Surfactant: Saponin 0.12 g / m ² Dye: D-2 18.9 mg / m ² Dye: D-3 67.2 mg / m ² Colloidal silica 0.3 g / m ² hardener: HA-1 110 mg / m ² Hardener: K 110 mg / m ² Backing protective layer formulation (5) Gelatin 1.0 mg / m ² Matting agent: average particle size 4. 0 μm polymethyl methacrylate 50 mg / m ² Surfactant: sodium sulfosuccinate di (2-ethylhexyl) ester 10 mg / m ² Hardener: HA-2 0.14 g / m ² Hardener: HA-3 100 mg / m ²

[0124]

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[0125]

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[0126]

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<< Preparation of Processing Agent >> (Prescription of Processing Solution) (1) Developing Concentrate (per liter)

[0128]

[Table 1]

* 1-Phenyl-4-hydroxymethyl-4-methyl-
3-Pyrazolidone At the time of use, water was added to the above-mentioned concentrated solution to make 2 l. The pH of the working solution is 10. Adjusted to 6.

(2) Fixing solution (per liter of working solution) Pure water 120 ml Ammonium thiosulfate (70% Na salt: manufactured by Hoechst) 260 g Sodium sulfite 22 g Boric acid 10 g Tartaric acid 3 g Sodium acetate trihydrate 32 g Acetic acid (90% aqueous solution) 16.5 g Aluminum sulfate / 18-hydrate 18 g Finished to 400 ml with 50% sulfuric acid aqueous solution and pure water. When using, 600 ml of pure water and 400 m of the above concentrated liquid
and l. The pH at the time of use is 4.7.

(3) Stabilized solution (per liter of working solution) DTPA 5 g Potassium sulfite 30 g 8-mercaptoadenine 0.1 g Compound K-1 0.1 g

[0132]

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Citric acid 10 g Sulfuric acid was added to adjust the pH at the time of use to 4.8. Add water to make the total volume 1 liter and use.

<< Running Processing >> The prepared photosensitive material was processed using the above-mentioned processing solution by using an automatic developing machine GR-2 manufactured by Konica Corporation.
A 6SR water washing system was modified to a three-stage countercurrent system. One unexposed sample and one whole-surface exposed sample were alternately processed so that the blackening ratio became 50% under the following processing conditions, and 100 m ^2. Was run. The stabilizing processing solution overflowing from the processing tank closest to the stabilizing processing solution fixing tank was used for diluting the concentrated fixing solution, and tap water was used as the water insufficient for dilution. The drying zone of the automatic developing machine had a far-infrared heater, and in order to prevent concentration of the developing solution and the fixing solution, 1 l of water corresponding to the evaporation of each water was added per day.

(Processing conditions) Temperature Time Replenishment rate (ml / m ² ) Development 38 ° C. 12 seconds 130 Fixing 38 ° C. 8 seconds 100 Stabilization 38 ° C. 10 seconds 300 Squeeze 2 seconds Drying 40 ° C. 10 seconds Total 42 seconds Line speed ( through an interference filter and wedge the conveying speed) 2200 mm / min <evaluation of sensitivity variations "760 nm, was white light exposure at 10 ^-5 seconds the sample,
The sensitivity was determined by the logarithm of the reciprocal of the exposure amount to obtain a density of 2.5. The change in sensitivity before and after running was measured.

<< Evaluation of Halftone Variation >> A sample exposed to DTT-3100 (manufactured by Dainippon Screen Co., Ltd.) so that halftone dots change stepwise is processed, and the halftone dot pattern (target 5
(0%). The change in net% before and after running was examined.

<< Evaluation of Fixing Failure >> After the completion of the running, the line speed of the automatic developing machine was increased to 4400 mm / min to carry out the processing, and the occurrence of the fixing failure was evaluated. A sample where silver halide escaped without any problem was evaluated as ○, a sample where a very small portion of the silver halide did not escape was generated, and a sample where a portion of the silver halide did not escape also appeared at the center.

<< Low Temperature Precipitating Property of Developed Concentrate >> The above-mentioned developed concentrates DL-1 to DL-6 were each placed in a 100 cc sample bottle, capped, and stored in a constant temperature room at -8 ° C. for one week. Thereafter, it was examined whether or not a solid precipitate was generated in the concentrated liquid. A sample without any precipitation was rated as ○, a sample with a very small amount of precipitation was rated as Δ, and a sample with a large amount of precipitate was rated as ×.

Incidentally, the measurement of the dot area was performed using X-Rite 3
61T (manufactured by Nippon Lithographic Equipment Co., Ltd.) was used, and the concentration was measured using a Macbeth densitometer.

The results are shown below.

Sample Developer Fluctuation in Sensitivity Fluctuation in Halftone Dot Variation in Fixing Low Temperature Precipitation 1 DL-1 -0.15 -3.5% × △ Comparison 2 DL-2 -0.12 -3.0% × △ Comparison 3 DL -3 -0.10 -2.2% XX Comparison 4 DL-4 -0.08 -1.9% △ Comparison 5 DL-5 -0.09 -2.0% × Comparison 6 DL-6 -0.010% ○ ○ Invention Example 2 <Preparation of Support> (Synthesis of Syndiotactic Polystyrene) Toluene 2
100 parts by weight of styrene, 100 parts by weight of styrene, 56 g of triisobutylaluminum, and 234 g of pentamethylcyclopentadienyltitanium trimethoxide were reacted at 96 ° C. for 8 hours. The catalyst was decomposed and removed with a methanol solution of sodium hydroxide, and then washed three times with methanol to obtain 34 parts by weight of a target compound (SPS).

(Preparation of SPS Film) Obtained SPS
Was melt-extruded from a T-die at 330 ° C. into a film and quenched and solidified on a cooling drum to obtain an unstretched film. At this time, the take-up speed of the cooling drum was performed in two stages, and the unstretched film having a thickness of
After preheating at ℃ and longitudinal stretching (3.1 times), transverse stretching at 130 ° C (3.4 times) and heat fixing at 250 ° C. As a result, the bending elastic modulus of the support was 450 kg / m.
A biaxially stretched film having a thickness of m ² and a thickness of 100 μm was obtained.

(Undercoat of SPS Film) After silica was vapor-deposited on both sides of the SPS film, an undercoat layer containing styrene-glycidyl acrylate and tin oxide fine particles and subjected to antistatic treatment was formed.

<Preparation of Photosensitive Material> (Preparation of Silver Halide Emulsion A) An average thickness of 70 mol% of silver chloride and the balance of silver bromide was 0.05 by a double jet method.
μm, silver chlorobromide core particles having an average diameter of 0.15 μm were prepared. At the time of mixing the core particles, K ₃ RuCl ₆ was added in an amount of 8 × 10 ⁻⁸ mol per mol of silver. The core particles were shelled using a double jet method. At that time, 3 × 10 ⁻⁷ mol of K ₂ IrCl ₆ was added per mol of silver. The obtained emulsion was silver / chloroiodobromide (90 mol% of silver chloride) having a core / shell type monodisperse (coefficient of variation: 10%) having a (100) plane as a main plane having an average thickness of 0.10 μm and an average diameter of 0.25 μm. , 0.2 mol% of silver iodobromide, the remainder being silver bromide). Then, JP-A-2-280139, 287
Desalting was performed using denatured gelatin G-8 (having the amino group in gelatin replaced with phenylcarbamyl) described on page (3).

The EAg after desalting was 190 mv at 50 ° C. 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻³ mol per mol of silver, potassium bromide and citric acid were added to adjust the pH to 5.6 and the EAg to 123 mV. After adding ^10-5 mol, 3 x 1 of inorganic sulfur was added.
0 ^-6 mol added to up sensitivity exits at temperature 60 ° C. chemically ripened.

After completion of ripening, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 ^-3 mol per mol of silver, and 1-phenyl-5-mercaptotetrazole was added in an amount of 3 × 10 3. -4 moles and gelatin were added.

(Preparation of Silver Halide Emulsion B) Using a double jet method, 60 mol% of silver chloride, 1.5 mol% of silver iodide, and the remainder made of silver bromide, having an average thickness of 0.05 μm and an average diameter of 0.1 mol.
15 μm silver chloroiodobromide core grains were prepared. At the time of mixing the core particles, K ₃ Rh (H ₂ O) Br ₅ was added in an amount of 2 × 1 per mole of silver.
^0-8 moles were added. The core particles were shelled using a double jet method. At that time, 3 × 10 ⁻⁷ mol of K ₂ IrCl ₆ was added per mol of silver.

The obtained emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (90 mol% of silver chloride, silver iodobromide having an average thickness of 0.10 μm and an average diameter of 0.42 μm). 0.3 mol%, the balance being silver bromide). Subsequently, desalting was performed using denatured gelatin G-8 (supra). The EAg after desalting was 180 mV at 50 ° C.

To the resulting emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 1 × 10 ⁻³ mol per mol of silver, and potassium bromide and citric acid were further added. The pH was adjusted to 5.6 and the EAg to 123 mV, and sodium thiosulfonate was added in an amount of 1 × 1 per mole of silver.
^0-4 mol and 2 × 10 ^-5 mol of chloroauric acid are added, and then 3 × 10 ^-5 mol of N, N, N′-trimethyl-N′-heptafluoroselenourea is added. Chemical ripening was performed until appeared.

After aging, 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver, 1-phenyl-5-mercaptotetrazole was added in an amount of 3 × 10 ⁻⁴ mol, and gelatin was added.

(Preparation of a silver halide photographic light-sensitive material for a printing plate making scanner for a He-Ne laser and a red semiconductor laser light source) On one undercoat layer of the above support, a gelatin undercoat layer of the following formula 1 was coated. The amount of gelatin is 0.5 g / m ²
The silver halide emulsion layer 1 having the following formula 2 was further provided thereon with a silver content of 1.5 g / m ² and a gelatin content of 0.5 g / m ² as an intermediate protective layer. Formula 3 below
The coating solution as the amount of gelatin is 0.3 g / m ^2, further amount of silver halide emulsion layers 2 formulations 4 thereon 1.
4g / m ^2, as the amount of gelatin is 0.4 g / m ^2, further amount of gelatin coating solution having the following formulation 5 is simultaneous multilayer coating so as to be 0.6 g / m ^2. On the other side of the undercoat layer, a backing layer of the following formulation 6 was coated with a gelatin amount of 0.6 g / m 2.
² , a hydrophobic polymer layer of the following formulation 7 was further formed thereon, and a backing protective layer of the following formulation 8 was further formed thereon at the same time as the emulsion layer side so that the amount of gelatin became 0.4 g / m ^2. A sample was obtained by coating.

Formulation 1 (Composition of gelatin undercoat layer) Gelatin 0.5 g / m ² Solid dispersed fine particles of dye AD-1 (average particle size 0.1 μm) 25 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² S-1 (Sodium-iso-amyl-n-decylsulfosuccinate) 0.4 mg / m ² Formulation 2 (Silver halide emulsion layer 1 composition) Silver halide emulsion A Silver amount 1.5 g / m ² Solid of dye AD-8 Dispersed fine particles (average particle size: 0.1 μm) 20 mg / m ² cyclodextrin (hydrophilic polymer) 0.5 g / m ² Hydrazine derivative H-7 20 mg / m ² Hydrazine derivative H-25 20 mg / m ² Sensitizing dye d- 1 5 mg / m ² sensitizing dye ^d-2 5mg / m 2 compound e 100 mg / m ² latex polymer f 0.5 g / m ² hardener ^{g 5mg / m 2 S-1} 0.7mg / m 2 2 Mercapto-6-hydroxy-purine 5 mg / m ² ethylenediaminetetraacetic acid (EDTA) 30 mg / m ² Colloidal silica (average particle size 0.05 .mu.m) 10 mg / m ² Formulation 3 (intermediate layer composition) Gelatin 0.3 g / m ² Redox compound : RE-1 10 mg / m ² S-1 2 mg / m ² Prescription 4 (Silver halide emulsion layer 2 composition) Silver halide emulsion B Silver amount 1.4 g / m ² Sensitizing dye d-1 Increased 3 mg / m ² sensitive dye ^d-2 3mg / m 2 nucleation accelerator Na 40mg / m ² 4 quaternary onium compound P-37 10mg / m ² 2- mercapto-6-hydroxy purine ^{5mg / m 2 EDTA 20mg / m} 2 latex polymer f 0 ^{.5g / m 2 S-1 1.7mg} / m 2 formulation 5 (emulsion protective layer composition) solid dispersion of gelatin 0.6 g / m ² dye AD-5 (average particle size 0.1 [mu] m) 40 ^{g / m 2 S-1 12mg} / m 2 Matting agent: average particle size 3.5μm monodisperse silica 25 mg / m ² nucleation accelerator Na 40mg / 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: K-2 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 Sodium polystyrene sulfonate 20 mg / m ² Compound i 100 mg / m ² Formulation 7 (hydrophobic polymer layer composition Latex (methyl methacrylate: acrylic acid = 97: 3) 1.0 g / m ² Hardener g 6 mg / m ² Formulation 8 (backing protective layer) Gelatin 0.4 g / m ² Matting agent: monodispersed polymethyl methacrylate having an average particle size of 5 μm 50 mg / m ² sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² surfactant h 1 mg / m ² dye k 20 mg / m ² HO (CH ₂ CH ₂ O) ₆₈ H 50 mg / m ² Hardener: K-2 20 mg / m ²

[0153]

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[0154]

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[0155]

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[0156]

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[0157] Note that the surface resistivity of the backing side after coating and drying is 23 ° C., at 6 × ^{10 11} in 20% RH, the film surface pH of the surface of the emulsion side is 5.5, the degree of swelling was 175.

Evaluation was made in the same manner as in Example 1.
Similar results were obtained.

Example 3 (Preparation of a silver halide photographic light-sensitive material sample for bright room turning) The average particle size of silver halide content of 99 mol% and silver bromide content of 1 mol% was 0.15 μm by a double jet method. And cubic silver chlorobromide particles were prepared. K ₃ Rh (H ₂ O) B during mixing
r ₅ was added 7 × 10 ^-5 mol per 1 mol of silver. Before the desalting step of removing soluble salts by a conventional method, 0.6 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added per mol of silver (hereinafter, referred to as “the salt”). Unless otherwise specified, the amount is based on 1 mol of silver). This emulsion was heated to 60 ° C., and TAI was 60 mg.
0.75 mg of sodium thiosulfate was added, and after 60 minutes from the addition of TAI, 600 mg of TAI was further added, and the temperature was lowered and set.

Then, a coating solution was prepared by adding an additive so as to be in the following amount per 1 m ^{2, and the} following emulsion layer coating solution was successively formed on one surface of the undercoated SPS support as in Example 2. The lower layer liquid of the protective layer was simultaneously coated with the following backing coating liquid on the opposite surface.

[0161] <Emulsion Coating Solution> 0.5 N NaOH solution 4.39 ml / m ² Compound i 6.53mg / m ² 4 quaternary onium compound: T-7 30mg / m ² Quillaja saponin 107 mg / m ² Compound B 18.5mg / m ² compound c 9.8 mg / m ² of gelatin latex 480 mg / m ² sodium polystyrenesulfonate 52.2 mg / m ² colloidal silica 20 mg / m ² <protective layer infranate> gelatin 0.5 g / m ² dye two solid Dispersion (average particle size 0.1 μm) 62.0 mg / m ² Citric acid 4.1 mg / m ² Hardener K 80 mg / m ² Hardener: K-2 60 mg / m ² Sodium polystyrene sulfonate 11.0 mg / m ² <upper protective layer solution> gelatin 0.3 g / m ² compound e 18.0 mg / m ² dye d 48.4 mg / m ² compound f 105.0mg m ² Compound DOO 1.25 mg / m ² amorphous silica (average particle diameter 1.63) 15.0 mg / m ² amorphous silica (average particle size 3.5 [mu] m) 21.0 mg / m ² Citric acid 4.5 mg / m ² Sodium polystyrene sulfonate 11.0 mg / m ^{2 In-} line addition of hardener K 10 mg / m ² <Backing coating solution> Compound H 170 mg / m ² Dye 30 mg / m ² Compound h 45 mg / m ² Compound n 10 mg / m ² Quillajasaponins 111 mg / m ² compound le 200 mg / m ² colloidal silica 200 mg / m ² compound o 35 mg / m ² compound follower 31 mg / m ² compound Ca 3.1 mg / m ² of polymethyl methacrylate acid polymer (average particle diameter 5.6μm) 28.9mg / m ² glyoxal 10.1 mg / m ² citric acid 9.3 mg / m ² polystyrenesulfonate Phosphate sodium 71.1 mg / m ² additive compound the following in-line Yo 81 mg / m ² Compound data 88.2mg / m ² of calcium acetate 3.0 mg / m ² Hardener: ^K-2 50mg / ^m 2

[0162]

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[0163]

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[0164]

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However, the coating amount was 2.5 g / silver in the emulsion layer.
gelatin amount 1.2 g / m ² m ^{2, and} the amount of gelatin backing layer is uniformly coated so as to be 2.1 g / m ^2.

A sample subjected to image exposure with a bright room printer P627FM using an electrodeless discharge tube light source manufactured by US Fusion Co., Ltd., was subjected to a test using a developing solution stored at 55 ° C. and 50% RH for 3 days. Evaluation was performed in the same manner as in Example 1.

The results are shown below.

Sample Developer Fluctuation in Sensitivity Fluctuation in Halftone Dot Variation in Fixing Low Temperature Precipitation 1 DL-1 -0.12 -5.5% × △ Comparison 2 DL-2 -0.10 -4.0% × △ Comparison 3 DL -3 -0.09 -3.3% XX comparison 4 DL-4 -0.05 -3.0% △ comparison 5 DL-5 -0.05 -3.0% △ comparison 6 DL-6 -0.010% ○ ○ The present invention

[0169]

According to the present invention, the concentration of the concentrated developing solution can be increased.

Claims (1)

[Claims] 1. A black-and-white silver halide photographic light-sensitive material comprising ascorbic acids and 1.8 mol / l or more of Na ions and having a sodium ratio Nr defined by the following formula of 0.6 or less. Developing composition. Nr = Na / (Na + K) [where Na is the amount of sodium ion (mol / l), K
Represents the amount (mol / l) of potassium ion. ]