JPH10260512A - Method for processing silver halide photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for processing the silver halide photosensitive material capable of obtaining a sufficiently low minimum density and reducing occurrence of silver sludge, even when the photosensitive material is processed in a small replenishing rate by executing imagewise exposure and development processing of the silver halide photosensitive material having a direct positive emulsion layer in the presence of a specified compound. SOLUTION: This silver halide photosensitive material is provided on a support with one prefogged direct positive silver halide emulsion layer and after imagewise exposure, it undergoes development processing in the presence of the compound represented by the formula in which each of D and E is a -CH= or -CH(R0 )= group or an N atom; R0 is a substituent; each of L1 -L3 is, independently, an H or halogen atom, or a substituent for forming a ring together with one of C, N, or 0 atom; at least one of L1 , L2 , L3 , and R0 is a -SM group; and M is an alkali metal atom or an H atom or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide light-sensitive material containing a previously covered silver halide emulsion, and more particularly to a method for processing a silver halide light-sensitive material with a small amount of replenishment for development. The present invention relates to a method for processing a silver halide light-sensitive material having a low minimum density and generating little silver sludge.

[0002]

2. Description of the Prior Art In the field of graphic arts, it is necessary that the minimum density of a silver halide light-sensitive material of a direct positive type, which is covered in advance, is sufficiently low. In this photosensitive material, silver halide grains previously covered by reacting silver halide grains with a reducing agent are photobleached during imagewise exposure, and the exposed portions become inactive and the unexposed portions become active. This utilizes a mechanism for inverting an image. Therefore,
If the photobleaching of the overlaid silver halide emulsion is sufficient, the exposed portion becomes inactive for development, and a sufficiently low minimum density can be obtained. However, since photobleaching usually does not completely occur and the silver halide grains are slightly covered, the minimum density may increase depending on the state of the developing solution, resulting in a so-called "missing defect". On the other hand, there is a demand for reducing the replenishment amount of the developing solution from the viewpoint of environmental protection, and in order to realize a low replenishment amount, it is necessary to prevent the development activity from deteriorating due to air oxidation or the like. To prevent the deterioration of the developer, it is necessary to use a large amount of sulfite, a preservative, of 0.3 mol / l or more. However, since sulfite has a dissolving effect on silver halide, there are two problems. May occur. First, a large amount of sulfite dissolves the silver halide grains,
This is a problem that the nuclei remaining in the interior or the like without being photo-bleached can be developed, resulting in "missing defects". Another problem is that silver is eluted from the photosensitive material as a silver sulfite complex in the developing solution, and this silver complex is reduced in the developing solution and adheres to and accumulates on the developing tank or roller as soon as the silver complex is reduced. This is called silver stain or silver sludge, which adheres to the photosensitive material to be processed to stain the image or contaminate the automatic developing machine itself, so that it is necessary to periodically clean and maintain the equipment.

As described in JP-A-56-24347 and JP-A-8-6215, a method for reducing such silver stains is to reduce silver ions eluted in a developer and / or to reduce silver ions. A method of adding a compound that suppresses the reduction of ions to silver is known. However, these materials have not yet achieved both a sufficiently low minimum density and a sufficient prevention of silver contamination.

It is known that a developer is supplied as a solid processing agent, and JP-A-61-259921 describes that the stability of the developer as a solid processing agent is improved.

[0005]

Accordingly, it is an object of the present invention to provide a sufficiently low minimum density even when a silver halide light-sensitive material containing a previously covered silver halide emulsion is processed with a small development replenishment amount. Accordingly, it is an object of the present invention to provide a method for processing a silver halide light-sensitive material which generates little silver sludge.

[0006]

The present invention has been attained by the following. (1) Imagewise exposure of a silver halide light-sensitive material having at least one pre-covered direct positive emulsion layer on a support, followed by development in the presence of the compound of the formula (I) during development A method for processing a silver halide photosensitive material.

[0007]

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In the general formula (I), D and E each represent a —CH ＝ group, a —C (R ₀ ) ＝ group, or a nitrogen atom, wherein R ₀ represents a substituent. L ₁ , L ₂ , and L ₃ each represent a hydrogen atom, a halogen atom, or a substituent bonded to a ring at a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, and L _{1 to} L ₃ are They may be the same or different. However
At least one of L ₁ , L ₂ , L ₃ and R ₀ is a —SM group (M is an alkali metal atom, a hydrogen atom, an ammonium group)
Having. When only one of E and D represents a nitrogen atom, E is a nitrogen atom and D is a -CH = group or-.
C (R ₀ ) = represents a group, and in this case L ₂ and L ₃ do not represent a hydroxy group. (2) The method for processing a silver halide photographic material as described in (1) above, wherein the replenishing amount of the developer is 320 cc or less per 1 m ^{2 of the} photographic material. (3) The method for processing a photographic light-sensitive material as described in (1) or (2) above, wherein the developing agent of the developer is substantially free of hydroquinone and comprises a compound represented by the general formula (II). .

[0009]

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In the general formula (II), Ra and Rb represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a mercapto group and an alkylthio group, respectively. P and Q each represent a hydroxy group, hydroxyalkyl group, carboxyl group, carboxyalkyl group, sulfo group, sulfoalkyl group, amino group, aminoalkyl group, alkyl group, alkoxy group, mercapto group, or P and Q Represents a group of atoms necessary to form a 5- to 7-membered ring together with two vinyl carbon atoms substituted by Ra and Rb and a carbon atom substituted by Y. Y is = O or = N-Rc
It is a group composed of Here, Rc represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group. (4) The method for processing a photographic light-sensitive material according to any one of the above (1) to (3), wherein the developer is prepared using a solid processing agent.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the formula (I) will be described in detail. L ₁ , L ₂ , substituents other than the hydrogen atom represented by L ₃ and the substituent represented by R ₀ , specifically,
Halogen atom (fluorine atom, chloro atom, bromine atom or iodine atom), alkyl group (including aralkyl group, cycloalkyl group, active methine group, etc.), alkenyl group, alkynyl group, aryl group, heterocyclic group, quaternary A heterocyclic group containing a nitrogen atom (eg, a pyridinio group), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a carboxy group or a salt thereof,
Sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (including a group containing a repeating ethyleneoxy or propyleneoxy unit) ), An aryloxy group, a heterocyclic oxy group, an acyloxy group, an (alkoxy or aryloxy) carbonyloxy group, a carbamoyloxy group, a sulfonyloxy group, an amino group, an (alkyl, aryl or heterocyclic) amino group, a hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamo Arylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonio groups, oxamoylamino groups, (alkyl or aryl) sulfonyl group, an acylureido group,
Acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl or heterocycle) thio group,
Including (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof, phosphoric acid amide or phosphate ester structure Groups, and the like.
These substituents may be further substituted with these substituents. E is a nitrogen atom and D is a -CH = group or-
When C (R ₀ ) = represents a group, L ₂ and L ₃ do not represent a hydroxy group.

The substituents other than the hydrogen atom represented by L ₁ , L ₂ and L ₃ and the substituent represented by R ₀ are more preferable.
A substituent having 0 to 15 carbon atoms, a chlorine atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a carboxy group or a salt thereof, a cyano group, an alkoxy group, an aryloxy group, an acyloxy group; Group, amino group, (alkyl, aryl or heterocycle)
Amino group, hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, nitro group, mercapto group, (alkyl,
An aryl or heterocycle) thio group, a sulfo group or a salt thereof, or a sulfamoyl group, more preferably an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a carbamoyl group or a salt thereof, an alkoxy group, Aryloxy group, acyloxy group, amino group, (alkyl, aryl or heterocycle) amino group, hydroxyamino group, N-substituted saturated or unsaturated nitrogen-containing heterocyclic group, acylamino group, sulfonamide group, ureido group, A thioureido group, a sulfamoylamino group, a mercapto group, a (alkyl, aryl, or heterocyclic) thio group, a sulfo group or a salt thereof, and most preferably an amino group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group , Alkylamino group, arylamino group, alkyl Thio, a Aruruchio group, a mercapto group, a carboxy group or a salt thereof, a sulfo group or a salt thereof. In the general formula (I), L ₁ , L ₂ , L ₃ and R ₀
May combine with each other to form a condensed ring in which a hydrocarbon ring, a hetero ring, or an aromatic ring is condensed.

In the general formula (I), at least one of L _{1 to} L ₃ and R ₀ has a —SM group. Here, M represents an alkali metal atom, a hydrogen atom, or an ammonium group. Here, the term “alkali metal atom” specifically refers to Na, K, Li,
Mg, Ca, etc., which exist as counter cations of -S-. M is preferably a hydrogen atom, an ammonium group, Na ⁺ or K ⁺ , and particularly preferably a hydrogen atom. Among the compounds of the general formula (I), the compounds represented by the following general formulas (A) and (B) are preferred.

[0014]

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In the general formula (A), R _{1 to} R ₄ represent a hydrogen atom, a halogen atom, or any substituent bonded to the ring by a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom, This is a group having the same meaning as L ₁ , L ₂ and L _{3 in} formula (I), and the preferred range is also the same. However, R ₁ and R ₃ do not represent a hydroxy group. R _{1 to} R ₄ may be the same or different, but at least one of them is a —SM group. M represents a hydrogen atom, an alkali metal atom, or an ammonium group.

In the general formula (A), at least one of R _{1 to} R ₄ is a —SM group, and more preferably, at least two of R _{1 to} R ₄ are a —SM group. When at least two of R _{1 to} R ₄ are —SM groups, preferably R ₄ and R ₁ , or R ₄
And R ₃ are —SM groups.

In the present invention, among the compounds represented by the general formula (A), the compounds represented by the following general formulas (A-1) to (A-3) are particularly preferred.

[0018]

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In the general formula (A-1), R_TenIs Mercap
X represents a hydrogen atom, a hydrogen atom, or an optional substituent;
Represents a substituent substituted with a functional group or a water-soluble group.
Y in the general formula (A-2)₁Is a water-soluble group or a water-soluble group
Represents a substituent substituted with ₂₀Is a hydrogen atom or any
Represents a substituent. Y in the general formula (A-3)_TwoIs a water-soluble group
Or a substituent substituted with a water-soluble group,₃₀Is water
Represents an atom or an optional substituent. Where R_TenAnd Y₁
Does not represent a hydroxy group.

Next, the compounds represented by formulas (A-1) to (A-3) will be described in detail. In the general formula (A-1), R ₁₀ represents a mercapto group, a hydrogen atom or any substituent. Here, the optional substituent means R _{1 to} R in the general formula (A).
_The same substituents as those described for the substituent other than the hydrogen atom in ₄ can be mentioned. R ₁₀ is preferably a mercapto group, a hydrogen atom, or a group selected from the following substituents having 0 to 15 carbon atoms. That is, examples include an amino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamide group, an alkylthio group, an arylthio group, an alkylamino group, and an arylamino group. In the general formula (A-1), X represents a water-soluble group or a substituent substituted with a water-soluble group. Here, the water-soluble group is a sulfonic acid or a carboxylic acid and a salt thereof, a salt such as an ammonio group, or a group containing a dissociable group which can be partially or completely dissociated by an alkaline developer. Has a sulfo group (or a salt thereof),
A carboxy group (or a salt thereof), a hydroxy group, a mercapto group, an amino group, an ammonium group, a sulfonamide group,
It represents an acylsulfamoyl group, a sulfonylsulfamoyl group, an active methine group, or a substituent containing these groups. In the present invention, the active methine group refers to a methyl group substituted with two electron-withdrawing groups, and specifically, dicyanomethyl, α-cyano-α-ethoxycarbonylmethyl, α-acetyl-α-ethoxy And groups such as carbonylmethyl.

The substituent represented by X in the general formula (A-1) is the above-mentioned water-soluble group or a substituent substituted by the above-mentioned water-soluble group. 0-15
, An alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, (alkyl, aryl or heterocyclic)
Amino group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, sulfamoylamino group, (alkyl, aryl or heterocycle) thio group,
(Alkyl, aryl) sulfonyl group, sulfamoyl group, amino group and the like, preferably an alkyl group having 1 to 10 carbon atoms (particularly a methyl group substituted with an amino group), an aryl group, an aryloxy group, an amino group, (Alkyl,
An aryl or heterocycle) amino group or an (alkyl, aryl or heterocycle) thio group.

Among the compounds represented by the general formula (A-1),
Further preferred are compounds represented by the following general formula (A-1-a).

[0023]

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Where R₁₁Is R in general formula (A-1)_TenSynonymous with
Yes, the preferred range is also the same. R ₁₂, R₁₃Each
Which may be the same or different, a hydrogen atom, an alkyl
Represents a group, an aryl group, or a heterocyclic group. Where R
₁₂And R₁₃At least one of the at least one
It has a water-soluble group. Here, a water-soluble group is a sulfo group (or
Or its salt), carboxy group (or its salt), hydro
Xy, mercapto, amino, ammonium, sulfo
Honamide group, acylsulfamoyl group, sulfonyls
Rufamoyl group, active methine group, or those containing these groups
And preferably represents a sulfo group (or a sulfo group
Salt), carboxy group (or its salt), hydroxy group,
And groups such as amino groups. R₁₂And R₁₃Is preferred
Or an alkyl group or an aryl group,₁₂and
R₁₃Is an alkyl group,
A substituted or unsubstituted alkyl group of the formulas 1 to 4 is preferable.
And its substituents are water-soluble groups, particularly sulfo groups (and
Is a salt thereof), a carboxy group (or a salt thereof),
A di- or amino group is preferred. R₁₂And R₁₃But
When it is a reel group, the aryl group has 6 to 1 carbon atoms.
A substituted or unsubstituted phenyl group of 0 is preferable, and
As the substituent, a water-soluble group, particularly a sulfo group (or
Salt), carboxy group (or its salt), hydroxy group,
Or an amino group is preferred. R₁₂And R₁₃Is alkyl
When representing a group or an aryl group,
To form a ring structure. Also, due to the annular structure
A saturated heterocycle may be formed.

In the general formula (A-2), Y ₁ represents a water-soluble group or a substituent substituted with a water-soluble group;
It is synonymous with X in 1). In the formula (A-2), the water-soluble group represented by Y ₁ or a substituent substituted by a water-soluble group is more preferably an active methine group or the following group substituted by a water-soluble group, Group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkyl group, and aryl group. More preferably, Y ₁ is an active methine group or an amino group (alkyl, aryl, or heterocycle) substituted with a water-soluble group, wherein the water-soluble group is a hydroxy group, a carboxy group or a salt thereof, or a sulfo group. Groups or salts thereof are particularly preferred. Particularly preferred as Y ₁ is a (alkyl, aryl, or heterocyclic) amino group substituted with a hydroxy group, a carboxy group (or a salt thereof), or a sulfo group (or a salt thereof), and —N (R ₂₁ ) (R ₂₂ ).
Here, R ₂₁ and R ₂₂ are each represented by the general formula (1-a)
It is a group having the same meaning as R ₁₂ and R _13, and the preferred range is also the same.

In the general formula (A-2), R ₂₀ represents a hydrogen atom or an optional substituent, and the optional substituent is the same as those described for R _{1 to} R _{4 in} the general formula (A). The same is given. R ₂₀ is preferably a hydrogen atom or a group selected from the following substituents having 0 to 15 carbon atoms.
That is, examples include a hydroxy group, an amino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamide group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, and a hydroxylamino group. R ₂₀ is most preferably a hydrogen atom.

In the general formula (A-3), Y_TwoIs a water-soluble group
Or a substituent substituted with a water-soluble group, R₃₀Is hydrogen field
Represents a child or an optional substituent. In general formula (A-3)
Y _Two, R₃₀Is Y in general formula (A-2)₁, The general formula (A
-2) R₂₀And the preferred range is also
Is the same.

Next, the general formula (B) will be described in detail. R _{5 to} R ₇ in the general formula (B) are
It has the same meaning as R _{1 to} R ₄ , and the preferred range is also the same. Among the compounds represented by the general formula (B),
The compound represented by -1) is particularly preferred.

[0029]

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In the general formula (B-1), R ₅₀ has the same meaning as R _{5 to} R _{7 in} the general formula (B), and more preferably X in the general formulas (A-1) to (A-3). It is a water-soluble group or a group substituted with a water-soluble group as defined for Y ₁ and Y ₂ . further,
Most preferably, the compound represented by formula (B-1) is a compound represented by formula (B-1-a).

[0031]

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In the general formula (B-1-a), R₅₁, R₅₂
Is R of the general formula (A-1-a)₁₂, R ₁₃A group equivalent to
The preferred range is also the same.

The following are specific examples of the compound represented by the general formula (I) of the present invention, but the present invention is not limited to these.

[0034]

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[0035]

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[0036]

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[0037]

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The addition amount of the compound of the formula (I) is 0.01 to 10 mmol, preferably 0.1 to 5 mmol, per liter of the developing solution (working solution). When added to a light-sensitive material, 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / mol A
g, preferably 1 × 10 ^{−4 to} 5 × 10 ⁻⁴ mol / mol Ag
It is.

The preservative used in the present invention includes sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like.
If a large amount of sulfite is added, it causes silver contamination in the developing solution. Especially preferably, it is 0.1 mol / liter or less.

The light-sensitive material of the present invention is a direct-positive silver halide light-sensitive material, and the emulsion used therein has a nucleus capable of trapping free electrons inside the silver halide, and its surface is previously fogged. Silver halide grains. At least one of salts of rhodium, ruthenium, osmium, rhenium or iridium is used as a free electron trap nucleus of this type of emulsion. For example, JP-B-43-4125, JP-B-43-2940
5, U.S. Patent Nos. 2401051 and 297614
No. 9, No. 3023102, British Patent No. 707704
No. 1097999, French Patent No. 1520824
No. 1520817, Belgian Patent No. 7132
Emulsions described in No. 72, No. 721567, and No. 681768 can be used.

The silver halide used in the present invention may have any composition, but is preferably silver bromide, silver chlorobromide or silver chloride. When a silver chlorobromide emulsion is used, the silver chloride content is preferably at least 50 mol%, more preferably at least 80 mol%. The particle size is between 0.10μ and 1.0μ, preferably between 0.12μ and 0.40μ. The silver halide grains in the photographic emulsion are regularly (cubic, octahedral, etc.)
Those having a gular crystal form are preferred. The narrower the particle size distribution is, the more preferable it is.
90% of the total number of particles in the particle size range, preferably 9%
A so-called monodisperse emulsion containing 5% is preferable.

The internal electron trap nucleus used in the present invention is formed by adding a salt compound of rhodium, ruthenium, osnium, rhenium or iridium in silver halide grains in an amount of 10 ^-7 to 10 ^-3 mol, preferably 10 ^-3 mol to 1 mol of silver halide. 1
It can be introduced by containing 0 ^-6 to 10 ^-4 mol.

The internal electron trap nucleus used in the present invention is preferably used in the form of a transition metal complex, and the transition metal complex is preferably a six-coordinate complex represented by the following general formula (III). General formula (III) [M (NY) _n L _(6-n) ] _m , wherein M is rhodium, ruthenium, osnium, rhenium, or iridium, L is a bridging ligand, and Y is oxygen Or sulfur.m = 0, -1,-
2, -3, and n = 0, 1, 2. Preferred specific examples of L other than nitrosyl and thionitrosyl bridging ligands include halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand. Ligands, selenocyanate ligands, tellurocyanate ligands, azide ligands and aquo ligands. If an aquo ligand is present, it preferably occupies one or two of the ligands. The above metal complex can be added to silver halide during the preparation of silver halide grains.
The timing of addition may be such that it is uniformly distributed throughout the silver halide grains, but is preferably added so as to be present in the inner shell of the silver halide grains.

The fogging method of the direct positive silver halide emulsion of the present invention may be a known method, and can be achieved by light or chemical treatment. Such fogging can be achieved in a number of ways, including chemical sensitization until fogging occurs, and particularly good results are obtained, for example, by the method described in Science Eto Industry, Photographic 28, January, 1957, pp. 57-65. Can be The silver halide grains are fogged by intense light, fogged by reduced fog, such as thiourea dioxide or stannous chloride, or fogged with gold or a noble metal compound. It is also possible to use a combination of a reducing agent with a gold compound or another metal compound that is more positive than silver, such as rhodium, platinum or iridium, for fogging silver halide grains.
In the direct positive photographic emulsion according to the present invention, silver halide grains subjected to reduced fogging and gold fogging, that is, silver halide grains fogged with both a reduced fogging agent and a gold fogging agent, have high sensitivity and Dmin reduction. It is preferred in that respect. The use of low concentrations of reducing and fogging agents in such combinations, respectively, yields unique fogged silver halide grains which have the property of rapidly losing fog by chemical bleaching. It is known that one equivalent of a reducing agent reduces one equivalent of silver halide to silver. In order to obtain fogged silver halide grains with the property of rapidly losing fog by bleaching,
Use much less than one equivalent of reducing fog agent. That is, the silver halide grains are used in a range of 1.0 × 10 ^{-6 to} 1.0 × 10 ^-1 mol per mol of silver halide for fogging. High concentrations of reducing agent result in a significant loss of photographic speed. Examples of reducing fog agents that can be used in the practice of this invention include hydrazine, phosphonium salts such as tetra (hydroxymethyl) phosphonium chloride, thiourea dioxide (these are U.S. Pat.
Nos. 2651; 2983609); stannous salts such as stannous chloride (see U.S. Pat. No. 2,487,850); polyamines such as diethylenetriamine (see U.S. Pat. No. 2519698); and polyamines such as spermine (US Patent No. 2,521,925);
Bis (β-aminoethyl) sulfide and its water-soluble salts (see US Pat. No. 2,521,926). The gold fogging agent used in the practice of the present invention is any gold salt used for fogging photographic silver halide grains, and is described, for example, in U.S. Pat. Nos. 2,399,083 and 2,642,361. Examples include potassium chloroaulite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride, eulosulfobenzothiazole, metochloride and the like. The concentration of the gold fogging agent used in the practice of the present invention can be varied in a wide range, but is generally in the range of 1.0 × 10 ^{−8 to} 1.0 × 10 ⁻⁴ mol per mol of silver halide.
Potassium chloroaurate is a particularly preferred gold fogging agent and is used at a concentration of about 5 mg or less per mole of silver halide, preferably at a concentration of about 0.5 to 4 mg per mole of silver halide. When a gold fogging agent is used in combination with a reducing fogging agent, it is preferred that the major part of the fogging agent combination be a gold fogging agent, and generally the ratio of gold fogging agent to reducing fogging agent is about 1: 3 to about 20: 1, but often from about 2: 1 to 20: 1. The silver halide grains are preferably fogged first with a reducing fogging agent and then with a gold fogging agent. However, the reverse is also possible, and a reducing fogging agent and a gold fogging agent can be used simultaneously. In the practice of the present invention, the silver halide grains can be fogged before coating or can be fogged after coating. The reaction conditions for fogging the silver halide grains can be varied widely, but generally the pH is about 5 to 7,
The pAg is about 7-9 and the temperature is about 40-100 ° C, most commonly in the range of about 50-70 ° C.

In the present invention, it is preferable to use a water-soluble dye or a solid-dispersible dye having a main absorption in the visible wavelength region of the inherent photosensitive wavelength region of the silver halide emulsion used. Among them, dyes having λmax in the range of 350 nm to 600 nm are preferred. There is no particular limitation on the chemical structure of the dye, and oxonol dyes, hemioxonol dyes, merocyanine dyes, cyanine dyes, azo dyes and the like can be used. Specifically, examples of the water-soluble dye include pyrazolone dyes described in JP-B-58-12576, pyrazolone oxonol dyes described in U.S. Pat. No. 2,274,782, and U.S. Pat. Diarylazo dyes described in US Pat. No. 3,423,207
Styryl dyes and butadienyl dyes described in U.S. Pat. No. 3,384,487, merocyanine dyes described in U.S. Pat. No. 2,527,583, and U.S. Pat. No. 3,486,89.
No. 7, No. 3,652,284, No. 3,718,4
No. 72 merocyanine dyes and oxonol dyes,
Enaminohemioxonol dyes described in U.S. Pat. No. 3,976,661 and British Patent Nos. 584,609 and 1,177,429, JP-A-48-85130,
Nos. 49-99620, 49-114420, U.S. Pat. Nos. 2,533,472 and 3,148,187
No. 3,177,078, No. 3,247,12
No. 7, No. 3,540,887, No. 3,575,7
No. 04 and 3,653,905 are used. The dye capable of being solid-dispersed in the form of microcrystals is added to a non-photosensitive layer provided between the emulsion layer and the support for the purpose of improving both tone reproducibility and tone variability. The coating amount of this dye is 10 per square meter.
mg-500 mg is preferable, and 50-300 mg is particularly preferable. The dye used in the present invention is described in International Patent WO88 / 0.
4794, European Patent EP 0274723 A1
Nos. 276,566, 299,435, JP-A-52-92716, 55-155350, 55
155351, 61-205934, 48-
No. 68623, U.S. Pat. Nos. 2,527,583 and 348
No. 6897, No. 3746539, No. 3933798
Nos. 4,130,429 and 4,408,411, Japanese Patent Application Nos. 1-50874, 1-103751, 1-30.
No. 7,363, and the like, and can be easily synthesized according to the method. In the direct-positive silver halide photographic light-sensitive material of the present invention, dyes which are solid-dispersed in layers other than those described above for safelight safety and other improvements as long as the effects of the present invention are not impaired. And / or water-soluble dyes can be added. A preferable addition amount is such that when added to the emulsion layer, the decrease in sensitivity due to the addition does not exceed 0.2 in logE.
100 mg / m ² .

The direct-positive silver halide photographic light-sensitive material of the present invention can contain various other commonly used photographic additives. As a stabilizer, for example, triazoles, azaindenes, quaternary benzothiazolium compounds, mercapto compounds, or water-soluble inorganic salts such as cadmium, cobalt, nickel, manganese, gold, thallium, and zinc may be contained. Further, as a hardening agent, for example, aldehydes such as formalin, glyoxal, and mucochloric acid, S-triazines, epoxies, aziridines, vinylsulfonic acid and the like, or as a coating aid, for example, saponin, sodium polyalkylene sulfonate, lauryl polyethylene glycol Or oleyl monoether,
Amylated alkyltaurine, fluorine-containing compounds, and the like may be contained. Further, a color coupler can be contained. In addition, if necessary, a whitening agent, an ultraviolet absorber, a preservative, a matting agent, an antistatic agent, and the like can be added. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have coating aids, antistatic, slipperiness improvement, emulsification / dispersion, adhesion prevention and photographic property improvement (eg, development acceleration, high contrast For various purposes such as sensitization), various surfactants may be contained. For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol /
Polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives ( Nonionic surfactants such as alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc .; alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfonate, alkyl Naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl Such as taurine, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, carboxy group, sulfo group, phospho group, sulfate group, phosphate group, etc. Anionic surfactants containing an acidic group; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic Quaternary ammonium salts, pyridinium,
Heterocyclic quaternary ammonium salts such as imidazolium,
And cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings. Particularly preferred surfactants used in the present invention are those having a molecular weight of 60 described in JP-B-58-9412.
Zero or more polyalkylene oxides.

The polyalkylene oxide compound used in the present invention is preferably an alkylene oxide having 2 to 4 carbon atoms, for example, ethylene oxide, propylene-1,2-oxide, butylene-1,2-oxide, and preferably at least ethylene oxide. Condensate of polyalkylene oxide consisting of 10 units with a compound having at least one active hydrogen atom such as water, aliphatic alcohol, aromatic alcohol, aliphatic, organic amine, hexitol derivative or two or more polyalkylenes And oxide block copolymers. That is, as the polyalkylene oxide compound, specifically, polyalkylene glycols, polyalkylene glycol alkyl ethers, polyalkylene glycol aryl ethers, polyalkylene glycol (alkylaryl) ethers, polyalkylene glycol esters, polyalkylene glycol fatty acid amides, polyalkylene Glycolamines Polyalkylene glycol / block copolymers, polyalkylene glycol graft polymers and the like can be used. The molecular weight needs to be 600 or more. The number of polyalkylene oxides is not limited to one in the molecule, but may be two or more. In that case, the individual polyalkylene oxides may consist of less than 10 alkylene oxide units, but the total number of alkylene oxide units in the molecule must be at least 10. When there are two or more polyalkylene oxides in the molecule, each of them may consist of different alkylene oxide units, for example ethylene oxide and propylene oxide. The polyalkylene oxide compound used in the present invention is preferably 1
It contains from 4 to 100 alkylene oxide units. When these polyalkylene oxide compounds are added to the silver halide emulsion, they are dissolved in an aqueous solution of an appropriate concentration or in a low-boiling organic solvent miscible with water, at an appropriate time before coating, preferably It can be added to the emulsion after chemical ripening. Non-photosensitive hydrophilic colloid layers, such as interlayers, protective layers,
You may add to a filter layer etc.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide or polymethyl methacrylate for the purpose of preventing adhesion to a photographic emulsion layer or other hydrophilic colloid layers. The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg, vinyl acetate), acrylonitrile, and the like can be used alone or in combination.

The emulsion used in the present invention mainly uses gelatin as a protective colloid, and it is particularly advantageous to use inert gelatin. Instead of gelatin, a photographically inert gelatin derivative (for example, phthalated gelatin) or a water-soluble synthetic polymer such as polyvinyl acrylate, polyvinyl alcohol, or polyvinylpyrrolidone is used. The silver halide emulsion of the present invention uses any suitable photographic support, for example, glass, film base such as cellulose acetate, cellulose acetate butyrate, polyester [for example, poly (ethylene terephthalate)] and the like. In particular, it is desirable to coat a vinylidene chloride copolymer on a polyester support, and apply a hydrophilic colloid layer thereon.

Here, the vinylidene chloride copolymer is 50
A copolymer containing vinylidene chloride in an amount of from 9 to 99.5% by weight, preferably 70 to 99% by weight.
A copolymer comprising vinylidene chloride / acrylic ester / vinyl monomer having an alcohol in a side chain described in JP-A-135526, and a copolymer comprising vinylidene chloride / alkyl acrylate / acrylic acid described in U.S. Pat. No. 2,852,378. Polymer, copolymer of vinylidene chloride / acrylonitrile / itaconic acid described in US Pat. No. 2,698,235, copolymer of vinylidene chloride / alkyl acrylate / itaconic acid described in US Pat. No. 3,788,856 Coupling, JP-A-2-24648, JP-A-2-246
And core / shell type vinylidene chloride copolymers described in JP-A Nos. 49 and 3-141346.

As a method for coating the vinylidene chloride copolymer on a polyester support, a solution in which these polymers are dissolved in an appropriate organic solvent, or an aqueous dispersion is applied by a well-known coating method such as dip coating. Law,
It can be applied by an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, or an extrusion coating method using a hopper described in US Pat. No. 2,681,294. . In addition, there is a so-called extrusion coating method in which a molten polymer is made to flow down into a moving polyester in a film form and is bonded by pressure simultaneously with cooling. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma for the surface of the polyester support to further improve the adhesive force between the polyester support and the polymer layer Processing such as treatment, high-pressure steam treatment, desorption treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment may be performed. In addition, U.S. Pat.
No. 5,937, No. 3,143,421, No. 3,5
Phenol and resorcinol as described in JP-A Nos. 01,301 and 3,271,178, and o-
A method of adding a polyester swelling agent such as cresol, m-cresol, trichloroacetic acid, dichloroacetic acid, monochloroacetic acid, chloral hydrate, benzyl alcohol, etc .; triazine crosslinking agents described in JP-A-3-10945 and JP-A-3-141347. The adhesive force can be improved by a method or the like. The polymer layer comprising the vinylidene chloride copolymer in the present invention has a thickness of 0.3 μ or more,
Preferably, the thickness is in the range of 0.5 to 3.0 μm.

The polyester is a polyester containing an aromatic dibasic acid and glycol as main components. Representative dibasic acids are terephthalic acid, isophthalic acid, p-
β-oxyethoxybenzoic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, adipic acid, sebacic acid, azelaic acid, 5-sodium sulfoisophthalic acid, diphenylenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and the like. Glycols include ethylene glycol, propylene glycol, butanediol, neopentylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-bisoxyethoxybenzene, bisphenol A, diethylene glycol, polyethylene glycol, etc. There is. Of the polyesters composed of these components, polyethylene terephthalate is the most convenient in terms of availability. The thickness of the polyester is not particularly limited, but is about 12 μm to 500 μm, preferably 40 μm.
Those having a size of about μ to 200 μ are advantageous in terms of ease of handling and versatility. In particular, those biaxially stretched and crystallized are advantageous in terms of stability and strength.

In order to improve the adhesive strength between the polymer layer and the emulsion layer, a layer having an adhesive property to both of them can be provided as an undercoat layer. Further, in order to further improve the adhesiveness, the surface of the polymer layer may be subjected to a conventional pretreatment such as corona discharge, ultraviolet irradiation, or flame treatment.

The following are specific examples of the compounds. [All numbers in parentheses indicate weight ratios. V-1 Copolymer of vinylidene chloride: methyl acrylate: hydroxyethyl acrylate (83: 12: 5) V-2 Copolymer of vinylidene chloride: ethyl methacrylate: hydroxypropyl acrylate (82: 10: 8) V-3 Copolymer of vinylidene chloride: hydroxydiethyl methacrylate (92: 8) V-4 Copolymer of vinylidene chloride: butyl acrylate: acrylic acid (94: 4: 2) V-5 Vinylidene chloride: butyl acrylate: itaconic acid (75 V-6: a copolymer of vinylidene chloride: methyl acrylate: itaconic acid (90: 8: 2) V-7: a copolymer of vinylidene chloride: itaconic acid monoethyl ester (96: 4) Combined V-8 Vinylidene chloride: acrylonitrile: acrylic acid (96: 3.5: 1. Copolymer of 5) V-9 Copolymer of vinylidene chloride: methyl acrylate: acrylic acid (90: 5: 5) V-10 Copolymer of vinylidene chloride: ethyl acrylate: acrylic acid (92: 5: 3) V-11 vinylidene chloride: methyl acrylate: 3-chloro-2-hydroxypropyl acrylate (84:
9: 7) V-12 Copolymer of vinylidene chloride: methyl acrylate: N-ethanol acrylamide (85: 10: 5) V-13 Copolymer of vinylidene chloride: methyl methacrylate: methyl acrylate: acrylonitrile: acrylic acid (9
0: 4: 4: 1: 0.5) Copolymer V-14 (core / shell type latex aqueous dispersion, core 80% by weight, shell 20% by weight) Core: vinylidene chloride: methyl meta Acrylate: methyl acrylate = 90: 5: 5 Shell part: vinylidene chloride: acrylonitrile: acrylic acid = 90: 5: 2.5

Hereinafter, processing agents such as a developing solution and a fixing solution, a processing method, and the like in the present invention will be described. There is no particular limitation on the developing agent used in the developer used in the present invention (hereinafter, both the development starting solution and the development replenisher are collectively referred to as a developer), but dihydroxybenzenes, ascorbic acid or derivatives thereof are used. And hydroquinone monosulfonate, which may be used alone or in combination. Further, from the viewpoint of developing ability, a combination of dihydroxybenzenes or ascorbic acid or a derivative thereof and 1-phenyl-3-pyrazolidone, or a combination of dihydroxybenzenes or ascorbic acid or a derivative thereof and p-aminophenol is preferable. Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone, and methylhydroquinone, with hydroquinone being particularly preferred.

The developing agent of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention includes 1-phenyl-3
-Pyrazolidone, 1-phenyl-4, 4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like. N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyphenyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine and the like as p-aminophenol-based developing agents used in the present invention Among them, N-methyl-p-aminophenol is preferred.

The dihydroxybenzene-based developing agent is usually 0.1.
It is preferably used in an amount of from 05 mol / l to 0.8 mol / l. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 mol / L to 0.6 mol / L, preferably 0.23 mol / L to 0.5 mol / L, It is preferred to use the latter in an amount of 0.06 mol / l or less, preferably 0.03 mol / l to 0.003 mol / l.

According to the processing method of the present invention, the preservative is that the developing solution contains substantially no hydroquinone and the compound represented by the general formula (II) (ascorbic acid or a derivative thereof) is used as a developing agent. From the viewpoint that there is no need to use a large amount of sulfite in terms of the effect of preventing silver contamination.

Next, the general formula (II) will be described in detail. In the general formula (II), Ra and Rb each represent a hydroxy group or an amino group (the substituent is an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an n-butyl group, a hydroxyethyl group, etc.) ), Acylamino group (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc. ), An alkoxycarbonylamino group (such as a methoxycarbonylamino group), a mercapto group,
Represents an alkylthio group (eg, methylthio group, ethylthio group). Preferred examples of Ra and Rb include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group.

P and Q are hydroxy, hydroxyalkyl, carboxyl, carboxyalkyl, sulfo, sulfoalkyl, amino, aminoalkyl,
Represents an alkyl group, an alkoxy group, a mercapto group,
Or, P and Q are bonded together with two vinyl carbon atoms substituted by Ra and Rb and a carbon atom substituted by Y,
Represents an atom group necessary for forming a 5- to 7-membered ring. As specific examples of the ring structure, -O-, -C (Rd) (Re)-, -C (Rf)
=, -C (= O)-, -N (Rg)-, -N =. However, Rd, Re, Rf, and Rg are a hydrogen atom and carbon number 1
And represents an alkyl group which may be substituted by 10 to 10 (substituents include a hydroxy group, a carboxy group and a sulfo group), a hydroxy group and a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- to 7-membered ring.

Examples of the 5- to 7-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring and a uracil ring. And as an example of a preferred 5- to 7-membered ring,
Dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolinone ring, azasiloxhexenone ring,
A uracil ring can be mentioned.

Y is a group composed of ＯO or NN-Rc. Here, Rc is a hydrogen atom, a hydroxyl group, an alkyl group (eg, methyl, ethyl), an acyl group (eg, acetyl), a hydroxyalkyl group (eg, hydroxymethyl, hydroxyethyl), a sulfoalkyl group (eg, sulfomethyl, sulfoethyl), a carboxyalkyl Represents a group (for example, carboxymethyl, carboxyethyl). Specific examples of the compound of the general formula (II) are shown below, but the present invention is not limited thereto.

[0063]

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[0064]

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Among them, preferred is ascorbic acid or erythorbic acid (a diastereomer of ascorbic acid).

The ascorbic acids used in the developer used in the present invention include an endiol type (Endiol), an enaminol type (Enaminol), an endamine type (Endiamin), a thiol-enol type (Thiol-Enol) and an enaminethiol type (E
namin-Thiol) is generally known as a compound. Examples of these compounds are described in U.S. Pat. No. 2,688,549 and JP-A-62-237443. The methods for synthesizing these ascorbic acids are also well known, and are described, for example, in Tsujio Nomura and Hirohisa Omura, "Reducton Chemistry" (Uchida Roizuruhoshinsha 1969). The ascorbic acids used in the present invention can be used in the form of alkali metal salts such as lithium salt, sodium salt and potassium salt.

The general range of the amount of the ascorbic acid of the general formula (II) is as follows.
10 ^-3 mol to 1 mol, particularly preferably 10 ^-2 mol to 0.1 mol.
5 moles.

It is preferable to use ascorbic acids as the main developing agent and 1-phenyl-3-pyrazolidone or a derivative thereof or a p-aminophenol derivative as the auxiliary developing agent. The most preferred combination is
It is a combination of an ascorbic acid derivative and a p-aminophenol derivative.

The 1-phenyl-3-pyrazolidone or a derivative thereof used in this embodiment includes those described above. Examples of the p-aminophenol-based developing agent include those described above, and N-methyl-p-aminophenol or aminophenols described in Japanese Patent Application Nos. 8-70908 and 8-70935 are disclosed. preferable.

When used in combination with an auxiliary developing agent,
Ascorbic acid derivative developing agent is usually 0.05 to 1.0
It is preferably used in an amount of mol / liter. Particularly preferably, it is in the range of 0.1 to 0.5 mol / liter. 1 mol of 1-phenyl-3-pyrazolidones or p-aminophenols as auxiliary developing agents was 0.2 mol /
It is preferably used in an amount of not more than 1 liter, more preferably not more than 0.1 mol / l.

The developer for processing the light-sensitive material in the present invention can contain commonly used additives (for example, a developing agent, an alkali agent, a pH buffer, a preservative, a chelating agent, etc.). These specific examples are shown below, but the present invention is not limited thereto. As a buffer used in the developer when developing the photosensitive material in the present invention,
Carbonate, boric acid described in JP-A-62-186259, JP-A-60-93
The sugars described in 433 (eg, saccharose), oximes (eg, acetoxime), phenols (eg, 5-sulfosalicylic acid), tertiary phosphates (eg, sodium salt, potassium salt), and the like, preferably carbonate , Boric acid is used. The amount of the buffer, particularly the carbonate, used is preferably at least 0.01 mol / l, particularly 0.05 to
1.5 mol / l.

The preservative used in the present invention includes sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like. More than 0.2 mol / l of sulfite, especially 0.3 mol / l
It is used in an amount of 1 liter or more, but if it is added in an excessively large amount, it causes silver contamination in the developing solution. Therefore, the upper limit is preferably 1.2 mol / l. Particularly preferably, 0.35-0.
7 mol / l. When ascorbic acids are used as a developing agent, the sulfite may be used in an amount of 0.5 mol / l or less, particularly 0.1 mol / l or less. As the preservative of the dihydroxybenzene-based developing agent, a small amount of the ascorbic acid derivative may be used in combination with a sulfite. Above all, it is preferable to use sodium erythorbate from the viewpoint of material cost. The amount added is preferably in the range of 0.03 to 0.12, more preferably in the range of 0.05 to 0.10.
When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Examples of the additives other than those described above include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide;
Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole and derivatives thereof, and heterocyclic mercapto compounds (eg, 3- (5-
Sodium mercaptotetrazol-1-yl) benzenesulfonate, 1-phenyl-5-mercaptotetrazole, and the compounds described in JP-A-62-212651 can also be added as physical development unevenness preventive agents.

Further, in addition to the compound of the present invention, a mercapto compound, an indazole compound, a benzotriazole compound, or a benzimidazole compound may be contained as an antifoggant or black pepper (black pepper) inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, Isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, sodium 4-((2-mercapto-1,3,4-thiadiazol-2-yl) thio) butanesulfonate, 5-amino-1,3,4 -Thiadiazole-2-thiol, chlorobenzotriazole, bromobenzotriazole,
Examples thereof include nitrobenzotriazole and methylbenzotriazole. The amount of these additives is usually 0.01 to 10 mmol, more preferably 0.05 to 2 mmol, per liter of the developer.

Further, various organic and organic compounds are contained in the developing solution of the present invention.
Inorganic chelating agents can be used alone or in combination. As the inorganic chelating agent, for example, sodium tetrapolyphosphate, sodium hexametaphosphate and the like can be used. On the other hand, as organic chelating agents, mainly organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be used. Examples of the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, acyelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. Acids, itaconic acid, malic acid, citric acid, tartaric acid and the like can be mentioned.

As the aminopolycarboxylic acid, for example,
Iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid,
1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic acid, and others JP-A-52-25632, 55-67747, 57-1
02624 and the compounds described in JP-B-53-40900.

Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acid described in, for example, US Pat.
May issue) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid,
Amino trimethylene phosphonic acid and the like, and the other Research Disclosure 18170, JP-A-57-
Compounds described in 208554, 54-61125, 55-29883, 56-97347 and the like can be mentioned.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A-52-102726, JP-A-53-42730, JP-A-54-121127 and JP-A-55-4
024, 55-4025, 55-126241, 55-65955, 55-6595
6 and the compounds described in Research Disclosure 18170 described above.

These organic and / or inorganic chelating agents are not limited to those described above. Also,
It may be used in the form of an alkali metal salt or ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ^{-4 to 1} × 10 ^-1 mol, more preferably ¹ × 10 ^{-3 to 1} × 10 ^-2 mol per liter of developer.

Further, in addition to the compound of general formula (I) as a silver stain inhibitor in a developer, a triazine having at least one mercapto group (for example, trimercaptotriazine, dimercaptotriazine, mercaptotriazine, 2-hydroxy-4 , 6-dimercaptotriazine, etc.) and the same pyrimidines (eg, 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-dimercaptopyrimidine, 5,6-
Diamino-2,4-dimercaptopyrimidine, 2,4,6-trimercaptopyrimidine and the like pyridine (eg, 2-mercaptopyridine, 2,6-dimercaptopyridine, 3,5-dimercaptopyridine, 2,4 , 6-trimercaptopyridine,
The compounds described in JP-A-7-248587), the same pyrazines (eg, 2-mercaptopyrazine, 2,6-dimercaptopyrazine, 2,3-dimercaptopyrazine, 2,3,5-trimercaptopyrazine, etc.), Pyridazine (eg, 3-mercaptopyridazine, 3,4-dimercaptopyridazine, 3,5-dimercaptopyridazine, 3,4,6-trimercaptopyridazine, etc.) and the same triazole (eg, mercaptotriazole, dimercaptotriazole, 1-methyl -2,5-dimercaptotriazole, etc.), the same thiadiazole (for example, 2-mercaptothiadiazole, 2,5-dimercaptothiadiazole and the like), compounds described in JP-A-7-175177,
For example, polyoxyalkyl phosphonates described in US Pat. No. 5,457,011 can be used. These silver stain inhibitors can be used alone or in combination of two or more, and the addition amount is preferably 0.05 to 10 mmol per 1 L of a developer.
0.1-5 mmol is more preferred. Further, compounds described in JP-A-61-267759 can be used as a dissolution aid.
Further, if necessary, a color tone agent, a surfactant, an antifoaming agent, a hardening agent and the like may be contained.

The preferred pH of the developer is from 9.0 to 10.8, particularly preferably from 9.5 to 10.8. As the alkali agent used for pH adjustment, a common water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.

As a cation of the developing solution, potassium ions do not suppress the development as compared with sodium ions, and there is less jaggedness around a blackened portion called a fringe. Furthermore, when stored as a concentrated solution, the potassium salt is generally preferred because of its higher solubility. However,
In the fixer, potassium ions inhibit fixation to the same extent as silver ions, so if the potassium ion concentration in the developer is high, the potassium ion concentration in the fixer will increase due to the developer being brought in by the photosensitive material. Is not preferred. From the above, the molar ratio of potassium ion to sodium ion in the developer is preferably between 20:80 and 80:20. The ratio of the potassium ion to the sodium ion can be arbitrarily adjusted within the above range using a counter cation such as a pH buffer, a pH adjuster, a preservative, and a chelating agent.

The replenishment amount of the developing solution was 32 per m ² of the photosensitive material.
0 ml or less is preferable, and 300 to 50 ml is more preferable. A good effect of the present invention can be obtained even with such a low replenishing amount, which is preferable from the viewpoint of reduction of waste liquid amount and environmental hygiene. The development replenisher has the same composition and / or
Alternatively, it may have a concentration, or may have a composition and / or concentration different from the starting solution.

As the fixing agent of the fixing agent in the present invention, ammonium thiosulfate, sodium thiosulfate and sodium ammonium thiosulfate can be used. The amount of the fixing agent can be changed as appropriate, but is generally from about 0.7 to about
3.0 mol / l.

The fixing solution in the present invention may contain a water-soluble aluminum salt and a water-soluble chromium salt acting as a hardener, and a water-soluble aluminum salt is preferable. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, aluminum lactate, and aluminum gluconate. These are preferably contained at 0.01 to 0.15 mol / l as the aluminum ion concentration in the working solution. When the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts including a hardening agent or the like as a separate part, or may be a one-part composition including all components.

If desired, preservatives (eg, sulfites, bisulfites, metabisulfites, etc.) may be used in the fixing treatment agent in an amount of 0.015
Mol / l or more, preferably 0.02 mol / l ~
0.3 mol / l), pH buffer (eg acetic acid, sodium acetate, sodium carbonate, sodium bicarbonate,
0.1 mol / L to 1 mol / L, preferably 0.2 mol / L, of phosphoric acid, succinic acid, adipic acid and the like
0.7 mol / liter), compounds with aluminum stabilizing or water softening ability (eg gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid) 0.005 g of benzoic acid, salicylic acid, tiron, ascorbic acid, glutaric acid, aspartic acid, glycine, cysteine, ethylenediaminetetraacetic acid, nitrilotriacetic acid and their derivatives and their salts, sugars, boric acid, etc.
1 mol / l to 0.5 mol / l, preferably 0.00
5 mol / l to 0.3 mol / l).

In addition, compounds described in JP-A-62-78551, pH adjusters (eg, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can be included. Examples of the surfactant include an anionic surfactant such as a sulfated sulfone oxide, a polyethylene-based surfactant, and an amphoteric surfactant described in JP-A-57-6840. Can also. Examples of the wetting agent include alkanolamine and alkylene glycol. As a fixing accelerator, JP-A-6-30
Alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in 8681, and JP-B-45-35754 and 58-12253.
5, thiourea derivatives described in 58-122536, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat.No. 4,216,459, JP-A-64-4739, JP-A-1-4739, and 1-159
645 and the mercapto compound described in 3-101728, 4-1
70539, which may comprise a thiocyanate.

The pH of the fixing solution in the present invention is 4.0 or more, preferably 4.5 to 7.0. The pH of the fixer is increased by mixing with a developer due to the treatment. In this case, the pH is 6.0 or less, preferably 5.7 or less for a hardened fixer, and 7.0 or less, preferably 6.7 or less for a non-hardened fixer.

The replenishment rate of the fixing solution is 50 per m ² of the photosensitive material.
0 ml or less, preferably 390 ml or less, more preferably 320 to 80 ml. The replenisher may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration than the starting solution.

The fixing solution can be reused by a known fixing solution regenerating method such as electrolytic silver recovery. By regenerating, the replenishment rate of the fixing solution can be reduced to 200 ml / m ² or less. As a reproducing apparatus, for example, there is a Reclaim R-60 manufactured by Fuji Hunt. It is also preferable to remove dyes and the like by using an adsorption filter made of activated carbon or the like.

When the developing and fixing agent in the present invention is a liquid, it is preferable to store it in a packaging material having a low oxygen permeability as described in, for example, JP-A-61-73147. Further, when these liquids are concentrated liquids, they are used after being diluted at a ratio of 0.2 to 3 parts of water to 1 part of the concentrated liquid so as to have a predetermined concentration.

[0093] Even if the developing agent and the fixing agent in the present invention are solidified, the same result as that of the liquid agent can be obtained. The solid preparation in the present invention may be in a known form (powder, granule, granule, lump, tablet, compactor, briquette, plate, rod, paste, etc.). These solid agents may be coated with a water-soluble coating agent or film to separate components that react with each other upon contact, or may separate components that react with each other in a multilayer structure. These may be used in combination.

Known coating agents and granulating auxiliaries can be used, but polyvinylpyrrolidone, polyethylene glycol, polystyrenesulfonic acid, and vinyl compounds are preferred. In addition, JP-A-5-45805, column 2, line 48 to column 3, column 1
The third line can be helpful.

When a plurality of layers are formed, components which do not react even if they come into contact with each other may be sandwiched between components which react with each other, and processed into tablets or briquettes. It may be packaged in a similar layer configuration. These methods are described, for example, in JP-A-61-259921, JP-A-4-16841,
4-78848 and 5-93991.

[0096] The bulk density of the solid processing agent is preferably 0.5 to 6.0 g / cm ^3, particularly tablets preferably 1.0 to 5.0 g / cm ^3, the granules is preferably 0.5 to 1.5 g / cm ^3.

As the method for producing the solid processing agent in the present invention, any known method can be used. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, and 4-328
37, 4-78848, 5-93991, JP-A-4-85533, 4-8553
4, 4-85535, 5-134362, 5-97070, 5-04098,
5-224361, 6-138604, 6-138605, Japanese Patent Application 7-89123
Etc. can be referred to.

More specifically, tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, spray drying, melt solidification, briquetting, roller compaction Ing method or the like can be used.

The solubility of the solid agent in the present invention can be adjusted by changing the surface state (smoothness, porousness, etc.), partially changing the thickness, or forming a hollow donut.
Further, a plurality of granules can be formed in a plurality of shapes in order to impart different solubilities to the plurality of granules or match the solubilities of materials having different solubilities. Also, multilayer granulated materials having different compositions on the surface and inside may be used.

The packaging material for the solid agent is preferably a material having low oxygen and moisture permeability, and the packaging material may be a known one such as a bag, a tube, or a box. Also, JP-A-6-242585-
6-242588, 6-247432, 6-247448, Japanese Patent Application 5-3066
4. A foldable shape as disclosed in JP-A-7-5664 and JP-A-7-5666 to 7-5669 is also preferable for reducing the storage space of the waste packaging material. These packaging materials
A screw cap, a pull top, an aluminum seal may be attached to the outlet of the treatment agent, or the packaging material may be heat-sealed, but other known materials may be used, and there is no particular limitation. Further, in terms of environmental conservation, it is preferable to recycle or reuse the waste packaging material.

The method for dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and a known method can be used. Examples of these methods include a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function, and a method disclosed in
A method of dissolving with a dissolving apparatus having a dissolving part and a part for storing a finished liquid as described in 7-235499, and replenishing from the stock part, JP-A-5-119454, JP-A-6-19102, JP-A-7-235499
-A method for supplying and dissolving a processing agent into the circulating system of an automatic developing machine as described in -261357, and dissolving by supplying a processing agent according to the processing of photosensitive material in an automatic developing machine with a built-in dissolving tank. However, any other known method can be used. The processing agent may be charged manually, or may be automatically opened and automatically loaded by a dissolving apparatus or an automatic developing machine having an opening mechanism as described in Japanese Patent Application No. 7-235498. The latter is preferred from an environmental point of view. Specifically, a method of piercing the outlet, a method of peeling, a method of cutting out, a method of pushing out, and a method disclosed in JP-A-6-1910
2, the method described in 6-95331, and the like.

The photosensitive material which has been subjected to the development and fixing processing is then washed or stabilized (hereinafter, unless otherwise specified, washing including the stabilization processing is performed. ). Water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing solution. These replenishing amounts are generally about 17 liters to about 8 liters per 1 m ² of the light-sensitive material, but the replenishing amounts can be smaller. In particular, when the replenishment amount is 3 liters or less (including 0, that is, washing with water), not only water saving processing can be performed, but also piping for installing an automatic developing machine can be eliminated. When washing with a small amount of water is performed, it is more preferable to provide a squeezing roller and a crossover roller washing tank described in JP-A-63-18350 and JP-A-62-287252. Various oxidizing agents (for example, ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) to reduce pollution load and prevent water scale, which are problems when washing with a small amount of water. You may combine addition and filter filtration.

[0103] As a method of reducing the replenishing amount of the washing, a multi-stage countercurrent system (for example, two stages, three stages, etc.) than the older are known, washing replenishing amount is preferably photosensitive material 1 m ² per 200 to 50 ml. This effect can be similarly obtained by an independent multi-stage system (a method in which a new solution is individually replenished in a multi-stage washing tank without using countercurrent).

Further, in the method of the present invention, a scale preventing means may be provided in the washing step. As the scale prevention means, known means can be used, and there is no particular limitation. There are a method of applying a magnetic field, a method of sonication, a method of applying heat, and a method of emptying the tank when not in use. These scale prevention means may be performed in accordance with the processing of the photosensitive material, may be performed at regular intervals irrespective of the use condition, or may be performed only during a period during which processing is not performed, such as at night. It may be applied to washing water in advance and replenished. Further, it is also preferable to perform different scale prevention means every certain period in order to suppress the generation of resistant bacteria. The protective agent is not particularly limited, and known agents can be used. In addition to the oxidizing agents described above, chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxides (for example, 2-
Mercaptopyridine-N-oxide, etc.) and may be used alone or in combination of two or more. As a method for energizing, JP-A-3-224685, JP-A-3-224687, JP-A-4-16280, 4-189
The method described in 80 or the like can be used.

In addition, a known water-soluble surfactant or antifoaming agent may be added to prevent water bubble unevenness and stain transfer. Further, a dye adsorbent described in JP-A-63-163456 may be provided in a washing system to prevent contamination by a dye eluted from the light-sensitive material.

A part or all of the overflow solution from the water washing step can be mixed with a processing solution having a fixing ability as described in JP-A-60-235133. In addition, microbial treatment (eg, sulfur oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramics), or oxidation treatment with an electric current or an oxidizing agent is carried out to obtain biochemical oxygen demand. Volume (BOD), chemical oxygen demand (COD), iodine consumption, etc. before draining, or forming a filter using a polymer with affinity for silver or forming a sparingly soluble silver complex such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment to lower the silver concentration in the wastewater by adding a compound to the mixture to precipitate silver and filtering the precipitate by a filter.

In some cases, a stabilization treatment may be performed after the water washing treatment. For example, Japanese Patent Application Laid-Open Nos. 2-201357 and 2-132435,
A bath containing a compound described in JP-A-1-102553 and JP-A-46-44446 may be used as the final bath of the light-sensitive material. If necessary, this stabilizing bath also contains an ammonium compound, a metal compound such as Bi or Al, a fluorescent whitening agent, various chelating agents, a membrane pH regulator,
Hardening agents, fungicides, sunscreens, alkanolamines and surfactants can also be added.

Additives such as deterrents and stabilizing agents to be added to the washing and stabilizing baths may be solid agents as in the above-mentioned developing and fixing agents.

It is preferable that the waste liquid of the developing solution, fixing solution, washing water, and stabilizing solution used in the present invention is incinerated. In addition, these waste liquids are, for example, Japanese Patent Publication No. 7-83867, US5439560
It is also possible to dispose after concentrating or liquefying or solidifying with a concentrating device such as described in US Pat.

To reduce the replenishment amount of the processing agent, it is preferable to reduce the opening area of the processing tank to prevent evaporation of the liquid and oxidation of the air. Roller transport type automatic developing machines are described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and are simply referred to as roller transport type automatic developing machines in this specification. This self-developing machine comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. Furthermore, during development and fixing and
A rinsing bath may be provided between the fixing water washing.

In the development processing of the present invention, the dry-to-dry 25 to 25
160 seconds is preferred, development and fixing time is 40 seconds or less, preferably 6 to 35 seconds, and the temperature of each solution is preferably 25 to 50 ° C., and 3
0-40 ° C is preferred. Washing temperature and time is 0-50 ℃
It is preferably 40 seconds or less. According to the method of the present invention, the photosensitive material which has been developed, fixed and washed with water may be squeezed with washing water, that is, dried through a squeeze roller. Drying is about
The drying is performed at 40 to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions. Any known drying method can be used, and there is no particular limitation.
15534, the same 5-2256, heat roller drying as disclosed in the same 5-289294, there is drying by far infrared, etc.
A plurality of methods may be used in combination.

The various additives used in the light-sensitive material of the present invention are not particularly limited, and for example, those described in the following places can be preferably used. Item This section 1) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to line 7, right lower column, line 7, JP-A-2-18542, page 2, lower left column, line 13 From page 4, line 18, lower right column. 2) Antifoggants JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, and JP-A 1-237538. Thiosulfinic acid compound described in Japanese Patent Publication No. 3) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 4) Compound having an acid group From page 6, lower right column, line 6 to page 19, upper left column, line 1 of JP-A-2-103536. 5) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column, line 15 Plasticizer to page 19, upper right column, line 15; 6) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17. 7) Dyes Dyes on page 17, lower right column, lines 1 to 18 of JP-A-2-103536, solid dyes described in JP-A-2-294638 and Japanese Patent Application No. 3-185773. 8) Binder JP-A-2-18542, page 3, lower right column, line 1 to line 20. 9) Black spot inhibitors Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 10) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (especially compound examples II-1 to II-26). 11) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to page 1, second page, lower left column, and EP 452772A.

[0113]

The present invention will be described in more detail with reference to the following Examples, which do not limit the embodiments of the present invention. Example 1 <Preparation of Emulsion> [Emulsion 1] A mixed aqueous solution of silver nitrate aqueous solution and potassium bromide was simultaneously added to an aqueous gelatin solution kept at 60 ° C. in the presence of 3 × 10 ⁻⁵ mol of rhodium chloride per mol of silver. A silver bromide monodispersed emulsion having an average grain size of 0.2 μm was prepared by adding the mixture at the speed for 30 minutes. The emulsion was desalted by flocculation, the pAg was adjusted to 6.5, and 3 mg of thiourea dioxide per mole of silver was added.
And aged until the best performance was obtained, causing fogging. This is designated as Emulsion 1.

[Emulsion 2] In the presence of 2 × 10 ^-5 mol of rhodium chloride per mol of silver in an aqueous gelatin solution kept at 50 ° C., an aqueous silver nitrate solution and a mixed aqueous solution of sodium chloride and potassium bromide were simultaneously added at a constant rate. For 30 minutes to prepare a silver chlorobromide monodispersed emulsion having an average grain size of 0.2 μm. (Cl composition 95 mol%) This emulsion was desalted by flocculation method,
Per mole of silver, 1 mg of thiourea dioxide and 0.6 mg of chloroauric acid were added and aged fog was obtained at 65 ° C. until maximum performance was obtained. This is Emulsion 2.

The following compounds were added to the above emulsion, and silver halide was coated on the following support including an undercoat layer so that the gelatin coating amount was 1.6 g / m ² and the silver coating amount was 2.7 g / m ^2. An emulsion layer was coated. Compound -C 2.5 mg / m ² Compound -G 28 mg / m ² Compound -H 1.6 mg / m ² Compound -I 1.9 mg / m ² Compound -J 16 mg / m ² Compound -K 36 mg / m ² Compound - L 240mg / m ²

An emulsion protective lower layer and an upper layer were coated on the above emulsion layer.

<Preparation of Emulsion Protection Lower Layer Coating Solution and Its Coating>
The following compound was added to the aqueous gelatin solution, and the mixture was coated so that the coated amount of gelatin was 1.1 g / m ² . Gelatin 1.1 g / m ² Compound -D 58 mg / m ² Compound -E 40 mg / m ² Compound -F 156 mg / m ² Compound -M 16 mg / m ² glacial acetic acid 5.5 mg / m ² Compound -N 24 mg / m ² KBr 16 mg / m ² compound -L 290 mg / m ² compound -P 130 mg / m ² compound -Q 43 mg / m ²

<Preparation of Emulsion Protection Upper Layer Coating Solution and Its Coating>
The following compounds were added to an aqueous gelatin solution, and the mixture was coated so that the coated amount of gelatin was 0.4 g / m ² . Gelatin 0.4 g / m ² Silica irregular matting agent (3-4 μ diameter) 38 mg / m ² Compound N 25 mg / m ² Compound U 3 mg / m ² Compound V 20 mg / m ² Compound K 5 mg / m ²

Then, the following conductive layer and back layer were simultaneously coated on the opposite side of the support.

<Preparation of Coating Solution for Conductive Layer and Its Coating> The following compound was added to an aqueous solution of gelatin, and the coating amount of gelatin was reduced to 76.
It was applied so as to be mg / m ² . SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 188 mg / m ² Gelatin 76 mg / m ² Compound-J 13 mg / m ² Compound-N 15 mg / m ² Compound-K 12 mg / m ²

<Preparation of back layer coating solution and its coating> The following compound was added to an aqueous gelatin solution, and coated so that the coated amount of gelatin was 2.8 g / m ² . Gelatin 2.8 g / m ² Polymethyl methacrylate fine particles (average particle diameter 1.5 μm) 15mg / m ² Compound -R 175 mg / m ² Compound -E 74 mg / m ² Compound -G 49 mg / m ² Compound -S 41 mg / m ² compound -J 25 mg / m ² compound -N 55 mg / m ² compound -T 5 mg / m ² glacial acetic acid 13 mg / m ² compound -U 10 mg / m ² sodium sulfate 228 mg / m ² compound -K 20 mg / m ² compound -P 102 mg / m ² Compound-Q 34 mg / m ²

(Support, Undercoat Layer) The first and second undercoat layers having the following composition were applied to both sides of a biaxially stretched polyethylene terephthalate support (thickness, 100 μm). <Undercoat first layer> Core-shell type vinylidene chloride copolymer I 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle size 3 μ) 0.05 g Compound W 0.20 g Colloidal Silica (Snowtec Z ZL: particle size 70-100 μm, manufactured by Nissan Chemical Co., Ltd.) 0.12 g 100 g by adding water and further 10 wt% KOH was added to adjust the coating solution to pH = 6, and the drying temperature was 180 ° C. 2 minutes, dry film thickness 0.9
It was applied to be μ.

<Undercoat second layer> Gelatin 1 g Methylcellulose 0.05 g Compound-X 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Compound-Y 3.5 × 10 ⁻³ g Acetic acid 0.2 g of water was added and 100 g of this coating solution was dried at 170 ° C. for 2 minutes to obtain a dry film thickness of 0.1 g.
It was applied to 1 μm. Thus, a sample was prepared.

[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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<Processing Method> The obtained sample was exposed to sensitometry through a step wedge with a Dainippon Screen P627 type printer. Next, these samples were subjected to a running test using an automatic developing machine FG680A manufactured by Fuji Photo Film Co., Ltd. The running conditions were as follows: half-exposed large-sized paper (50.8 cm x 60.1 cm) films were processed 40 times a day, the replenishment rate of the developing solution and the fixing solution was set to 160 ml / m ² , 6L / m
Running for 6 days, treated as ² , and resting for one day, one round was performed, and six rounds were performed. The formulations of the developer and fixer used are shown below. It was shown to. The processing conditions were a developing time of 20 seconds and a developing temperature of 38 ° C.

The composition per liter of the concentrated solution of the developer (1) is shown below. Potassium hydroxide 105.0 g Diethylenetriamine / pentaacetic acid 6.0 g Potassium carbonate 120.0 g Sodium metabisulfite 120.0 g Potassium bromide 9.0 g Hydroquinone 75.0 g 5-Methylbenzotriazole 0.25 g 4-Hydroxymethyl-4- Methyl-1-phenyl-3-pyrazolidone 1.35 g Compound of general formula (I) The concentration in the working solution is described in Table 1. Sodium erythorbrate 9.0 g Diethylene glycol 60.0 g pH 10.7 Dilute 2 parts water to 2 parts. The pH of the working solution is 10.5.

The following silver stain inhibitors were used for comparison.

[0132]

Embedded image

The formula for 1 L of the concentrated solution of the fixing solution (1) is shown below. Ammonium thiosulfate 360.0 g Ethylenediamine tetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 33.0 g Sodium metasulfite 57.0 g Sodium hydroxide 37.2 g Acetic acid (100%) 90.0 g Tartaric acid 8 0.7 g sodium gluconate 5.1 g aluminum sulfate 25.2 g pH 4.85 In use, 1 part of the above concentrated solution is diluted with 2 parts of water. The pH of the working solution is 4.8.

As ammonium thiosulfate (compact), a flake product prepared by a spray-drying method was press-compressed with a roller compactor and crushed into amorphous chips of about 4 to 6 mm in size, and was blended with anhydrous sodium thiosulfate. For other bulk powders, general industrial products were used. 10 L of both the A agent and the B agent were filled in a foldable container made of high-density polyethylene, and the outlet of the A agent was sealed with an aluminum seal. The mouth of the B agent container was sealed with a screw cap. Japanese Patent Application No. 7-2354 for dissolution and replenishment
99, a dissolution replenishing apparatus having an automatic opening mechanism disclosed in Japanese Patent Application No. 7-235498 was used.

<Evaluation Method of Photographic Properties>
Change in sensitivity after round running and minimum density (Dmin),
The silver stain was evaluated. Here, the reciprocal of the exposure amount giving a density of 1.5 was defined as the sensitivity. Silver stain is visually observed for the generation of sludge in the developing tank and on the developing roller,
In addition, Fuji Photo Film's paper sensitive material KU-150
WP (6 cm × 30.3 cm) was treated, and the degree of dirt was visually evaluated on a 10-point scale. "10" is the best and "1" is the worst. "10" to "6" are practically usable, "5" is poor but practically practical, and "4" to "1" are levels that are not practical.

[0136]

[Table 1]

In the treatment methods of Experiments Nos. 1 to 9 and 12 to 20 of the present invention, the fluctuation in sensitivity to running fatigue liquid is small, the minimum concentration is low, and the degree of silver stain is low and good.

Example 2 An experiment similar to that of Example 1 was carried out using a solid developer (developer (2)).
And using a solid fixing agent (fixing solution (2))
Similar results were obtained. The compound of the general formula (1) is shown in Table 1.
It was evaluated in the same manner as in the above.

The composition of the solid developer (developer (2)) is shown below. Sodium hydroxide (beads) 99.5% 11.5 g Potassium sulfite (raw powder) 63.0 g Sodium sulfite (raw powder) 46.0 g Potassium carbonate 62.0 g Hydroquinone (briquette) 40.0 g Diethylenetriamine / pentaacetic acid 2.0 g 5-Methylbenzotriazole 0.35 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.5 g Compound of formula (I) Used in Table 1 Describe the concentration in the solution. 3- (5-Mercaptotetrazol-1-yl) sodium benzenesulfonate 0.1 g sodium erythorbate 6.0 g potassium bromide 6.6 g Dissolve in water to make 1 L. pH 10.65

Here, in the form of raw materials, the raw powder was used as a general industrial product, and the alkali metal salt beads used were commercially available products. When the raw material was in the form of a briquette, a plate-like material obtained by pressurizing and compressing using a briquetting machine was crushed and used. For minor components, each component was blended before briquetting. 10 L of the above treating agent was filled in a high-density polyethylene foldable container, and the outlet was sealed with an aluminum seal. For dissolution and replenishment, a dissolution and replenishment device having an automatic opening mechanism disclosed in Japanese Patent Application Nos. 7-235499 and 7-235498 was used.

The composition of the solid fixing agent (fixing solution (2)) is shown below. Agent A (solid) Ammonium thiosulfate (compact) 125.0 g Anhydrous sodium thiosulfate (raw powder) 19.0 g Sodium metabisulfite (raw powder) 18.0 g Anhydrous sodium acetate (raw powder) 42.0 g B Agent (Liquid) Ethylenediamine / tetraacetic acid / 2Na / dihydrate 0.03 g Citric anhydride 3.7 g Sodium gluconate 1.7 g Aluminum sulfate 8.4 g Sulfuric acid 2.1 g Dissolve in water to make 50 mL . The A agent and the B agent were dissolved in water to make 1 L. pH 4.8

Example 3 An experiment similar to that of Example 1 was performed using the following developer, and similar results were obtained. The compound of the general formula (I) is shown in Table 1.
Used as in. As shown in Table 2, the experiment of the present invention
In the treatment methods of Nos. 23 to 31 and 34 to 42, the sensitivity variation with running fatigue fluid is small, the minimum concentration is low, and the degree of silver stain is low and good.

[0143]

[Table 2]

<Developer Composition> Diethylenetriamine-5 acetic acid 2 g Potassium carbonate 33 g Sodium carbonate 28 g Sodium bicarbonate 25 g Sodium erythorbate 45 g N-methyl-p-aminophenol 7.5 g KBr 2 g 5-methylbenzotriazole 0.004 g 1- Phenyl-5-mercaptotetrazole 0.02 g Compound of general formula (1) The concentration in the working solution is described in Table 1. Sodium sulfite 2 g Water is added to 1 liter, and the pH is adjusted to 9.7.

[0145]

According to the present invention, a sufficiently low minimum density can be obtained even when a silver halide light-sensitive material containing a previously covered silver halide emulsion is processed with a small development replenishment amount.
A silver halide photosensitive material can be processed with less generation of silver sludge.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03C 5/31 G03C 5/31

Claims (4)

[Claims] A silver halide light-sensitive material having at least one pre-covered direct positive emulsion layer on a support is imagewise exposed and then developed in the presence of a compound of the formula (I) during development. A method for processing a silver halide photosensitive material. Embedded image In the general formula (I), D and E each represent -CH =
A group, —C (R ₀ ) = group or a nitrogen atom, wherein R ₀ represents a substituent. L ₁ , L ₂ , L ₃ each represent a hydrogen atom, a halogen atom, or a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a substituent bonded to the ring at any of phosphorus atoms,
L _{1 to} L ₃ may be the same or different. Where L ₁ , L ₂ ,
At least one of L ₃ and R ₀ has a —SM group (M is an alkali metal atom, a hydrogen atom, an ammonium group).
When only one of E and D represents a nitrogen atom, E represents a nitrogen atom and D represents a -CH = group or -C (R ₀ ) = group, and in this case, L ₂ and L ₃ represent hydroxy. It does not represent a group. 2. The replenishing amount of the developer is 32 per m ^{2 of} the photosensitive material.
2. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the pressure is 0 cc or less. 3. The method according to claim 1, wherein the developing agent of the developing solution is substantially free of hydroquinone and comprises a compound represented by the general formula (II). Embedded image In the general formula (II), Ra and Rb are each a hydroxy group,
Represents an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a mercapto group, or an alkylthio group. P and Q are each a hydroxy group,
Represents a hydroxyalkyl group, a carboxyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group, an alkoxy group, or a mercapto group; Represents the group of atoms necessary to form a 5- to 7-membered ring together with two vinyl carbon atoms substituted with Y and a carbon atom substituted with Y. Y is a group composed of ＝ O or ＮN-Rc. Here, Rc represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group. 4. The development processing method according to claim 1, wherein the developer is prepared using a solid processing agent.