JPH1165043A - Processing method for silver halide photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve a drying property of a sensitive material, eliminate persistent color, and prevent rust from being produced at a metallic part, by causing silver halide particles to adsorb specific benzimidazolocarbocyanine pigment and by processing them with a specific fixer. SOLUTION: Silver halide particles included in a silver halide emulsion layer adsorb benzimidazolocarbocyanine pigment expressed by an expression and is processed with a fixer containing at least 0.15 mol/lit. of succinic acid. In the expression, R11 and R12 are alkyl radicals and at least one of them denotes an alkoxyalkyl radical. R13 and R14 are alkyl radicals and at least one of them denotes a sulfoalkyl radical. X11 to X14 , which can be all the same or can be different from one another, denote a hydrogen atom, a cyano radical, a halogen- substituted alkyl radical, or a halogen atom, and one of the X11 and the X13 denotes a hydrogen atom. Z denotes ions necessary for balancing charge and n1 is 1 or 2, but is 1 when an intramolecule salt is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for processing a silver halide photographic material.

[0002]

2. Description of the Related Art A commonly used black-and-white silver halide photographic material is developed, and an image is formed by a process comprising fixing, washing and drying steps. Among the processing solutions used in these steps, in particular, conventional fixing solutions contain thiosulfate as a fixing agent, sulfite as a preservative thereof, acetic acid, boric acid, and the like as a pH buffer. Generally contains a hardener composed of a water-soluble aluminum salt. When using these fixers,
From the viewpoint of environmental protection and the like, when the replenishment rate per unit area of the silver halide photographic light-sensitive material is reduced, the drying property of the silver halide photographic light-sensitive material is deteriorated and the residual color is generated. Also, with the conventional fixing solution composition, there is a problem that the metal part of the automatic developing machine itself is corroded by a very small amount of gas generated from the fixing solution during operation of the automatic developing machine. Generally, exhausting a small amount of gas to the outside is performed, and the mechanism of the automatic developing machine becomes complicated or the number of parts increases.

[0003]

The problem to be solved by the present invention is to reduce the replenishment rate of the fixing solution per unit area of the silver halide photographic light-sensitive material and to increase the chemical oxygen demand (so-called CO). .D.) And a high biological oxygen demand (so-called BOD), while reducing the economical burden of wastewater treatment of the fixing wastewater and obtaining good drying properties even in such a low replenishment treatment. It is an object of the present invention to provide a method for processing a silver halide photographic light-sensitive material which has no residual color, and does not rust the metal part of the automatic developing machine without particularly exhausting the automatic developing machine.

[0004]

The above objects are achieved by the present invention described below. (1) A method for processing a silver halide photographic material having an at least one silver halide emulsion layer on a support by using an automatic developing machine to develop, fix, wash and dry the silver halide photographic material. The silver halide grains contained in the silver halide emulsion layer contain at least one of a benzimidazolocarbocyanine dye represented by the general formula (I):
A method for processing a silver halide photographic light-sensitive material, wherein the processing is performed with a fixing solution containing at least 0.15 mol / l of succinic acid, the type being adsorbed.

[0005]

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[In the general formula (I), R ₁₁ and R ₁₂ each represent an alkyl group, and at least one of R ₁₁ and R ₁₂ represents an alkoxyalkyl group. R ₁₃ and R ₁₄ each represent an alkyl group, and at least one of R ₁₃ and R ₁₄ represents a sulfoalkyl group. X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ may be the same or different and each represent a hydrogen atom, a cyano group, a halogen-substituted alkyl group, or a halogen atom, and at least one of X ₁₁ and X ₁₃ Represents a hydrogen atom. Z represents an ion necessary to balance the charge, and n ₁ is 1 or 2, and 1 when an internal salt is formed. (2) method for processing a silver halide photographic light-sensitive material of (1) to the replenishment rate of the silver halide photographic light-sensitive material 1 m ² per fixer for processing in the following 250 ml. (3) 70% or more of the total projected area of the silver halide grains of the silver halide photographic light-sensitive material has an average aspect ratio of 4 to 20.
The method for processing a silver halide photographic material according to the above (1) or (2), wherein

[0007]

Embodiments of the present invention will be described below in detail. The silver halide photographic light-sensitive material of the present invention has at least one silver halide emulsion layer on a support, and silver halide grains in the silver halide emulsion layer are represented by the general formula (I). At least one of the benzimidazolocarbocyanine dyes is adsorbed. Such a silver halide photographic light-sensitive material is processed by an automatic developing machine, and the fixing solution used in this processing contains succinic acid in an amount of 0.15 mol / l or more.

By using a benzimidazolocarbocyanine dye represented by the general formula (I) as a sensitizing dye and using a fixing solution containing succinic acid in an amount of 0.15 mol / L or more, the replenishment amount of the fixing solution can be reduced. Even under reduced conditions, residual color is small and good drying properties are obtained. Also, there is no rust on the metal part of the automatic developing machine. Furthermore, since the replenishment of the fixer can be reduced, the amount of waste of the fixer having a high chemical oxygen demand and a high biological oxygen demand decreases,
This is preferable in terms of environmental conservation, and the cost required for waste liquid treatment is reduced.

On the other hand, sensitizing dyes of the general formula (I)
When a dye other than the above is used, the residual color becomes a problem even if the dye has a similar structure. In addition, the content of succinic acid is 0.1
If the amount is less than 5 mol / liter, the drying property under low replenishment conditions deteriorates, and the level becomes practically unacceptable.

[0010] In addition, in the case of acetic acid which has been widely used in the past, rust is remarkably generated on a metal portion. Further, in order to obtain the same effect as that of the present invention, the amount of use must be increased, and the condition is such that rust is easily generated on the metal part.

In the present invention, from the viewpoint of reducing the amount of waste of the fixing solution, 1 m of the silver halide photographic light-sensitive material of the fixing solution is used.
The replenishment amount per ² is preferably 250 ml or less. In order to improve the photographic performance such as sensitivity and the fixing property, a silver halide emulsion containing tabular grains having an average aspect ratio of 4 to less than 20 and 70% or more of the total projected area of the silver halide grains is used. The silver halide photographic material used is preferably used.

Japanese Patent Application Laid-Open No. 63-284546 discloses "containing thiosulfate and having an acetate ion content of 0.33.
And less than 0.04 mol / l of at least one compound selected from citric acid, tartaric acid, malic acid, succinic acid and salts of these compounds.
A fixing solution for a silver halide photographic light-sensitive material, comprising: Is disclosed.

JP-A-5-127323 discloses that a fixing composition comprising at least a fixing agent, a preservative, a hardening agent and an acid agent contains succinic acid or maleic acid as an acid agent. Characteristic fixing composition. "

However, in the above publication, unlike the present invention,
There is no disclosure of processing a silver halide photographic light-sensitive material using a benzimidazolocarbocyanine dye represented by the general formula (I), and the light-sensitive material used in the examples is not disclosed. Is a merocyanine dye, which is completely different from the dye of the general formula (I). Further, there is no description about the replenishment conditions of the fixing solution, and unlike the present invention, there is no mention of the effect of preventing residual color and the effect of improving the drying property under low replenishment conditions.

In the present invention, when an organic acid such as citric acid, tartaric acid or malonic acid other than succinic acid disclosed in JP-A-63-284546 is used instead of succinic acid,
The solubility is not sufficient, and in particular, it becomes impossible to add an amount for eliminating residual color and improving drying properties under low replenishment conditions, which is not suitable for use.

In addition, when maleic acid disclosed in Japanese Patent Application Laid-Open No. 5-127323 is used, the effect of preventing residual color and improving the drying property can be obtained when the replenishing amount is increased, but sufficient effect under low replenishing conditions. I can't get it. Further, if an attempt is made to increase the amount of addition in order to obtain a sufficient effect, it will not be dissolved.

As described above, in the present invention, the effects of the present invention can be obtained only by using succinic acid, and cannot be obtained by other organic acids disclosed in the above publication.

The effect of the present invention is to provide an emulsion layer containing high silver chloride tabular grains and having a swelling ratio of 70% to 20%.
It is improved by using a photosensitive material regulated to 0% or less, and efficient drying is realized by drying the photosensitive material with an infrared radiating object and / or a heat roller at 70 ° C. or more.

In the present invention, at least one kind of a benzimidazolocarbocyanine dye represented by the general formula (I) is adsorbed on the silver halide grains contained in the silver halide emulsion layer.

[0020]

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In the formula, R ₁₁ and R ₁₂ represent a substituted or unsubstituted alkyl group, and at least one of R ₁₁ and R ₁₂ represents an alkoxyalkyl group. R ₁₃ and R ₁₄ represent a substituted or unsubstituted alkyl group, and at least one of R ₁₃ and R ₁₄ represents a sulfoalkyl group. X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ may be the same or different and each represent a hydrogen atom, a cyano group, a halogen-substituted alkyl group, or a halogen atom, and at least one of X ₁₁ and X ₁₃ Represents a hydrogen atom. Z represents an ion necessary to balance the charge, and n ₁ is 1 or 2. It is 1 when an intramolecular salt is formed.

The benzimidazolocarbocyanine dye represented by formula (I) will be described in detail. Where R ₁₁ , R
₁₂ represents a substituted or unsubstituted alkyl group. At least one of them is an alkoxyalkyl group (having 2 to 2 carbon atoms).
0, preferably 2 to 8, more preferably 2 to 5. Specific examples include a methoxymethyl group, a methoxypropyl group, an ethoxymethyl group, and an ethoxyethyl group. ), And preferably at least one is an ethoxyethyl group. The remaining one of R ₁₁ and R ₁₂ is preferably a methyl group or an ethyl group. R ₁₃ and R _{14 each} represent a substituted or unsubstituted alkyl group, and at least one of them preferably has 1 to 1 carbon atoms.
7, more preferably a sulfoalkyl group which is not substituted with an aromatic group having 1 to 4 carbon atoms. R ₁₃ and R ₁₄
The remaining one has 1 to 18 carbon atoms, preferably 1 to 7,
More preferably, it is a substituted or unsubstituted alkyl group of 1 to 4 (eg, methyl, ethyl, propyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl). Examples of the substituted alkyl group include a fluorine-substituted alkyl group (2,2-difluoroethyl group, 2,2
2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, etc., hydroxylalkyl group (hydroxymethyl group, hydroxyethyl group , An hydroxyalkyl group, etc.), an aralkyl group (benzyl, 2-phenylethyl etc.), a carboxyalkyl group (carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl etc.), an alkoxyalkyl group (2-methoxy Ethyl, 2- (2-methoxyethoxy) ethyl, etc.), sulfoalkyl group (2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- (3-sulfopropoxy) ethyl, 2-
Hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl, etc.), sulfatoalkyl group (3-
Sulfatopropyl, 4-sulfatobutyl, etc.), a hetero-substituted alkyl group ((2-pyrrolidin-2-one-1-
Il) ethyl, tetrahydrofurfuryl, 2-morpholinoethyl, etc.), 2-acetoxyethyl group, carboxymethoxymethyl group, 2-methanesulfonylaminoethyl group, allyl group.

X ₁₁ , X ₁₂ , X ₁₃ , and X ₁₄ may be the same or different, and each represents a hydrogen atom, a halogen atom (such as chlorine, bromine, or fluorine), a cyano group, or a haloalkyl group (trifluoromethyl, 2,2, -Difluoroethyl, 2,2
2, - trifluoroethyl, 2,2,3,3-tetrafluoro-propyl, etc.) are either, it is preferable that at least one is a hydrogen atom for X _11, X _13, for X _12, X ₁₄ Is a cyano group, a haloalkyl group,
It is preferably one of halogen atoms. Z represents an ion necessary for neutralizing the charge, and n ₁ is 1 or 2. When forming an inner salt, n ₁ is 1
It is.

Specific examples of the substituent in the compound of the formula (I) are shown in Table 1, but the present invention is not limited to these compounds.

[0025]

[Table 1]

The compound of the formula (I) of the present invention may be added in any manner as long as it is before the coating step. More specifically, a method of adding a silver halide emulsion at the time of preparing a coating solution for a photosensitive emulsion layer, a method of adding a silver halide grain at the time of silver halide grain formation, a method of adding a silver halide emulsion in a desalting step, and a method of chemical ripening (chemical sensitization) of a silver halide emulsion There is a method of adding immediately before the process, a method of adding during silver halide emulsion chemical ripening, and the like.
The compound before the chemical sensitization is preferable, and most preferably, the compound of the general formula (I) is added before the addition of the gold sensitizer and the chalcogen sensitizer described later, that is, before the chemical sensitization with these compounds. Further, it is also possible to add the compound of the general formula (I) at a temperature of 25 ° C. or more and less than 55 ° C., raise the temperature above the addition temperature, and carry out chemical ripening to uniformly coat each of the halogenated particles.

In order to incorporate the spectral sensitizing dyes represented by the general formula (I) used in the present invention into the silver halide emulsion of the present invention, they may be directly dispersed in the emulsion or may be dispersed in water. , Methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, It may be added to the emulsion by dissolving it in a solvent alone such as 1-methoxy-2-propanol, N, N-dimethylformamide or a mixed solvent. Also, U.S. Patent No. 3,469,987
JP-B-46-241 discloses a method of dissolving a dye in a volatile organic solvent, dispersing the solution in water or a hydrophilic colloid, and adding the dispersion to an emulsion.
As described in No. 85, etc., a method of dispersing in a water-soluble solvent without dissolving a water-insoluble dye and adding this dispersion to an emulsion, JP-B-44-23389, JP-B-44-27555 As described in JP-B-57-22091, a method of dissolving a dye in an acid and adding this solution to an emulsion, or adding an acid or a base to an aqueous solution in the presence of an acid or a base to add to an emulsion, US Patent 3,822,135, U.S. Pat.No. 4,006,025, etc., a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion in the presence of a surfactant, JP-A-53-102733, As described in JP-A-58-105141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion, as described in JP-A-51-74624, a red shift Dissolve the dye using the compound to be
A method of adding this solution to the emulsion can also be used. Also, ultrasonic waves can be used for dissolution. Preferred is a method in which a solid is dispersed in a water-soluble solvent, particularly water, and the dispersion is added to the emulsion.

The addition amount of the compound of the general formula (I) of the present invention is preferably 0.1 mmol or more and less than 10 mmol, more preferably 0.2 mmol or more and less than 3.0 mmol, more preferably 0.2 mmol or more and 2 mmol per 1 mol of silver. 0.5 mmol or less is preferred.
These dyes may be used alone or in combination of two or more.

In addition to these sensitizing dyes of the present invention, at least one selected from oxazolocarbocyanine dyes and monomethine cyanine dyes may be used in combination.

The silver halide grains of the present invention may have different phases in the inside and the surface layer or may consist of a uniform phase. Further, grains whose latent image is mainly formed on the surface (for example, a negative emulsion) may be used, and grains whose main image is mainly formed inside the grains (for example, an internal latent image type emulsion, a directly-inverted emulsion previously fogged) ). Preferably, the particles are such that the latent image is mainly formed on the surface. In forming such silver halide grains, in order to control the growth of the grains, a silver halide solvent such as ammonia, rodankari, rodanammon, thioether compound (for example, US Pat. No. 3,271,15)
No. 7, No. 3,574,628, No. 3,704, 1
No. 30, No. 4,297,439, No. 4,276
No. 374) thione compounds (for example, JP-A-53-1443)
No. 19, No. 53-82408, No. 55-77737
No.), amine compounds (for example, JP-A-54-100717)
No.) can be used.

In the course of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt, or an iron complex salt may be used.

The silver halide which can be used in the silver halide emulsion may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide and silver chloroiodobromide. The amount is preferably 0.003 mol or less per mol of silver. The AgI distribution may be an internal high concentration or an external high concentration. In the present invention, silver chlorobromide and silver chloride emulsions are preferably used. In particular, the silver chloride content is preferably at least 10 mol% with respect to 1 mol of silver.

Most of the silver halide grains usable in the silver halide emulsion are preferably tabular. The proportion of tabular grains contained in the silver halide grains contained in the emulsion layer is preferably at least 50%, more preferably at least 70%, in terms of projected area. The average aspect ratio of a tabular grain is given by the average value of the ratio of the diameter of a circle having an area equal to the projected area of each tabular grain to the thickness of each tabular grain. In this case, the average aspect ratio may be determined from the ratio between the average diameter and the average thickness. In the present invention, the particle aspect has an average aspect ratio of preferably 3 or more and less than 30, more preferably 4 or more and less than 20, and particularly preferably 4 or more and 15 or less. Further, the average thickness of the particles is preferably 0.3 μm or less, particularly preferably 0.2 μm or less. The lower limit is not particularly limited, but is about 0.05 μm.

Tabular silver halide emulsions of silver bromide or silver iodobromide are described in JP-A-58-127927 and JP-A-58-127927.
It can be easily prepared by referring to the methods described in JP-A-113927 and JP-A-58-113828. Also, pBr
In an atmosphere having a relatively low pBr value of 1.3 or less, a seed crystal in which tabular grains are present in an amount of 40% or more by weight is formed.
It can also be obtained by growing a seed crystal while simultaneously adding silver and a halogen solution while maintaining the Br value. In this growth process, it is desirable to add a silver and halogen solution so that no new crystal nuclei are generated. The size of the tabular silver halide grains can be adjusted by controlling the temperature, selecting the type and amount of the solvent, and controlling the addition rate of the silver salt and halide used during grain growth.
Further, tabular silver halide emulsions having a silver chloride content of 10 mol% or more based on silver are described in JP-B-64-8324, JP-B-64-8325, JP-B-64-8326, and JP-B-3
It can be prepared using the method described in JP-A-14328.

The silver halide used in the present invention is more preferably a tabular grain having a silver chloride content of at least 20 mol% and at least 50% of the total projected area having a {100} plane as a main plane. .

Japanese Patent Application Laid-Open Nos. 5-281640 and 5-31 disclose tabular grains having a {100} plane as a main plane.
3273, JP-A-6-59360, JP-A-6-30
No. 8648, JP-A-6-308649, JP-A-7-1
No. 46522, JP-A-7-104430, JP-A-7-104430
225441, JP-A-8-12954, JP-A-8-
It can be prepared by referring to the method described in Japanese Patent Application No. 122953 and Japanese Patent Application No. 8-96883.

The emulsion layer of the present invention contains 1.
It is preferable to contain a thiocyanate compound in an amount of 0 × 10 ⁻³ mol or more and less than 2.0 × 10 ⁻² mol, and more preferably 1.0 × 10 ⁻³ mol or more and 1.0 × 10 ⁻² mol or less. Addition of thiocyanic acid compound can be used for grain formation, physical ripening, grain growth,
It may be carried out in any process of chemical sensitization and coating, but addition before chemical sensitization is preferred. As the thiocyanate compound used during the preparation of a silver halide emulsion in the present invention, a water-soluble salt such as a metal thiocyanate or an ammonium salt can be generally used. Care should be taken to use a metal element that does not affect, and potassium and sodium salts are preferred. Also, A
A sparingly soluble salt such as gSCN may be added in the form of fine particles. In this case, the size of the AgSCN fine particles is preferably 0.2 μm or less in diameter, particularly preferably 0.05 μm or less. The lower limit is not particularly limited, but is about 0.01 μm.

The silver halide emulsion used in the present invention can be subjected to chemical sensitization. Chemical sensitization methods include sulfur sensitization, selenium sensitization, reduction sensitization with complex salts and polyamines, gold sensitization with gold compounds, and sensitization with metals such as iridium, platinum, rhodium, and palladium. For example, a known method can be used. These may be used in combination as needed. In particular, the sulfur sensitization method using a sulfur-containing compound and / or the selenium sensitization method using a selenium-containing compound are preferably performed in the presence of a compound that adsorbs to silver halide. The compound adsorbed on silver halide as used herein means a spectral sensitizing dye or a kind of photographic stabilizer, and is described in JP-A-63-305343.
And compounds disclosed in JP-A-1-77047 and the like. In the present invention, in order to adsorb the sensitizing dye of the general formula (I) to silver halide, it is preferable to perform the chemical sensitization in the presence of the dye represented by the general formula (I).

The silver content of the light-sensitive material of the present invention is preferably 0.5 to 5 g / m ² (per one side), and more preferably 0.8 to 2.0 g / m ² (per one side).

Next, the fixing solution used in the present invention contains succinic acid in an amount of 0.15 mol / L or more, preferably 0.15 mol / L or more.
It contains 0.50 mol / l, and the replenishment amount per m ^{2 of} the photographic material is preferably 250 ml or less, more preferably 25 to 250 ml, and particularly preferably 50 to 20 ml.
It is preferable to carry out the fixing process with 0 ml.

By using such a fixing solution,
Even when the processing under the low replenishment conditions described above is performed, the photosensitive material has good drying properties, has no residual color, and has no rust on the metal part of the automatic developing machine. On the other hand, when the content of succinic acid is less than 0.15 mol / liter, the effect of the present invention cannot be obtained as described above, and when the content is too large, the effect is not so much improved and the effect is not so large. If the concentration is too high, it is impossible to prepare a concentrated solution due to limitations due to solubility.

It is preferable that the replenishing amount of the fixing solution be within the above range. When the replenishing amount is small, the silver halide in the light-sensitive material is dissolved and the concentration in the fixing solution becomes high, The accumulation of the sensitizing dye and the like in the fixing solution becomes excessive and causes stains, which is not preferable. On the other hand, if the replenishment amount is large, the amount of waste liquid of the fixing solution having high chemical oxygen demand and biological oxygen demand becomes large, which is not preferable from the viewpoint of environmental conservation and the cost required for waste liquid treatment is increased.

The succinic acid used in the present invention may be a salt, and the salt is preferably an alkali metal salt (such as a lithium salt, a sodium salt, or a potassium salt), or an ammonium salt.

The fixing solution used in the present invention is an aqueous solution containing a thiosulfate, and preferably has a pH of 4.2 or more, and more preferably has a pH of 4.8 to 6.2. Examples of the thiosulfate include sodium thiosulfate and ammonium thiosulfate. The amount used can be appropriately changed, and is generally from 0.3 to 1.5 mol / l.

The fixing solution of the present invention contains a sulfite (including bisulfite) as a preservative in an amount of 0.01 to 0.30.
It is contained in the range of mol / liter. Examples of the sulfite include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, and potassium metabisulfite.

The fixing solution may contain a water-soluble aluminum salt acting as a hardening agent, and examples thereof include aluminum chloride, aluminum sulfate, and potassium alum. When adding the water-soluble aluminum salt,
Usually, the range of 0.01 to 0.15 mol / liter is preferable.

In the fixing solution, tartaric acid, citric acid, gluconic acid or derivatives thereof can be used alone or in combination of two or more. It is effective that these compounds contain 0.005 mol or more per liter of the fixing solution, and in particular, they contain 0.1 mol.
01 mol / l to 0.03 mol / l is particularly effective. However, these compounds are used for stabilizing aluminum, and as described above, do not have a function replacing succinic acid of the present invention since a large amount cannot be added.

Preferably, the fixing solution of the present invention does not substantially contain acetic acid (including salts). That is, the content of acetic acid is preferably 0.10 mol / l or less, more preferably 0 to 0.05 mol / l.

In the fixing solution of the present invention, for example, boric acid can be used as a pH buffer, and sodium hydroxide or sulfuric acid can be used as a pH adjuster. Further, a chelating agent having a water softening ability or a compound described in JP-A-62-78551 can be contained.

The fixing processing temperature and the fixing processing time in the fixing processing are 4 to 48 seconds at 20 ° C. to 50 ° C., respectively.
It is preferably 7 to 40 seconds at 25 ° C to 40 ° C, and more preferably 8 to 25 seconds at 32 ° C to 38 ° C.

The contents, replenishment amounts, and the like in the above are those used as used solutions.

The fixing solution of the present invention can be used as a concentrated solution for reducing transportation costs and storage space. When the concentrated solution is used as a transport solution, the concentration is preferably 4 times or less, and more preferably 3 times or less, for the purpose of preventing precipitation of the fixing solution components at low temperatures. The components can also be stored in several parts. At this time, the storage container has an oxygen permeability of 50 ml / m ² at 20 ° C. and 65% RH.
Atm day or less, usually those made of a material of 1.0 to 50 ml / m ² atm day can also be used.

The fixing solution can also be prepared by using a solid chemical, that is, a powdery fixing agent, and supplying it.

The developing agent used in combination with the fixing solution of the present invention or the developing agent preferably used is an ascorbic acid-based developing agent or a dihydroxybenzene-based developing agent. Of these, ascorbic acid-based developing agents are preferred. Specific examples of the compounds include the following. L-ascorbic acid D-ascorbic acid L-erythroascorbic acid D-glucoascorbic acid 6-deoxy-L-ascorbic acid L-rhamnoascorbic acid D-glucoheptoascorbic acid imino-L-erythroascorbic acid imino-D- Glucoascorbic acid Imino-D-glucoheptoascorbic acid Sodium isoascorbate L-Glycoascorbic acid D-Galactascorbic acid L-Alaboscorbic acid Sorboascorbic acid Sodium ascorbate

On the other hand, dihydroxybenzene-based developing agents include hydroquinone, hydroquinone monosulfonic acid, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone,
2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,
5-dimethylhydroquinone and the like.

In the present invention, the above-mentioned ascorbic acid-based developing agent or dihydroxybenzene-based developing agent may be used together with 1
It is preferable to use an auxiliary developing agent such as -phenyl-3-pyrazolidone or p-aminophenol in combination. In particular, in the present invention, it is preferable to use an ascorbic acid-based developing agent in combination with such an auxiliary developing agent.

The 1-phenyl-3-pyrazolidones include 1-phenyl-3-pyrazolidone, 1-phenyl-
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-
Pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone and the like.

Examples of p-aminophenols include N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, and 2-methyl-p-aminophenol. Examples include aminophenol and p-benzylaminophenol. Further, N, N-disubstituted aminophenols described in Japanese Patent Application No. 8-70908 can be used. The developing agent in the developer is usually preferably used in an amount of 0.01 mol / l to 0.8 mol / l, particularly preferably in an amount of 0.05 mol / l to 0.5 mol / l. preferable.

When an ascorbic acid-based developing agent or a dihydroxybenzene-based developing agent is used in combination with an auxiliary developing agent such as 1-phenyl-3-pyrazolidone or p-aminophenol, the former is used in an amount of 0.05 mol / liter. 0.5 to 0.5 mol / l, the latter being 0.001 to 0.
06 mol / l (particularly 0.003 to 0.06 mol / l
Liters).

The developer or the developer preferably contains a sulfite as a preservative. As sulfites,
Sodium sulfite, potassium sulfite, lithium sulfite,
Ammonium sulfite, sodium bisulfite, potassium metabisulfite, and the like. The sulfite in the developer is 0.0
It is preferably at least 3 mol / l. The upper limit is preferably up to 1.0 mol / l, especially up to 0.8 mol / l.

The developer or the developer may contain an amino compound for promoting development. In particular, JP-A-56-10624
No. 4, JP-A-61-267759 and JP-A-2-208652 may be used.

The pH of the developer is from 8.0 to 13.0, preferably from 8.3 to 12, more preferably from 8.5 to 1
0.5.

The developer or the developing solution has a pH value for setting.
It is preferable to contain a carbonate (for example, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate) as a pH buffer. The amount of the carbonate used in the present invention is preferably 0.1 mol / L or more, particularly preferably 0.3 mol / L or more and 2 mol / L or less, and more preferably 0.4 mol / L or more and 1 mol / L. The following are most preferred.

As the alkaline agent used for setting the pH of the developer or the developing solution, in addition to the above-mentioned carbonates, ordinary water-soluble inorganic alkali metal salts (eg, sodium hydroxide, potassium hydroxide, etc.) may be used. it can.

The developer or the developer further includes boric acid,
Borax, dibasic sodium phosphate, dibasic potassium phosphate,
PH like sodium monophosphate and potassium monophosphate
A buffer, and furthermore, a pH buffer described in JP-A-60-93433 can be used. Further, potassium bromide, a development inhibitor such as potassium iodide, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol,
Organic solvents such as methanol, diethylene glycol and triethylene glycol, benzotriazole derivatives,
Nitroindazole and the like can be used. Benzotriazole derivatives include 5-methylbenzotriazole, 5-bromobenzotriazole, 5-chlorobenzotriazole, 5-butylbenzotriazole, benzotriazole, and the like. 5 for nitroindazole
-Nitroindazole, 6-nitroindazole, 4-
There are nitroindazole, 7-nitroindazole, 3-cyano-5-nitroindazole and the like.

Further, if necessary, a color tone agent, a surfactant and the like may be contained.

The developer or the developer may contain a chelating agent. Specific examples of the compound include the following compounds. That is, ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid,
Nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1,3-diaminopropanoltetraacetic acid, triethylenetetraminehexaacetic acid Acetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, nitrilotrimethylenephosphonic acid,
-Hydroxyethylidene-1,1-diphosphonic acid, 1,
1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,3,3-tricarboxylic acid, catechol-3,5-disulfonic acid, Examples thereof include sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate. Particularly preferred are, for example, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, glycol etherdiaminetetraacetic acid, and hydroxyethylethylenediaminetriacetic acid. 2-phosphonobutane-1,2,4-tricarboxylic acid, 1,1-diphosphonoethane-2-carboxylic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraphosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydro Shipuropiriden 1,1-diphosphonic acid, 1-amino-1,1-diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and salts thereof.

It is preferable that potassium ion is 10 mol% or more and 90 mol% or less, sodium ion is 10 mol% or more and 90 mol% or less, and sodium ion is 20 mol% or less of all cations contained in the developer. Not less than 50 mol%, potassium ion is not less than 50 mol% and not more than 80 mol%.
More preferably, it is at most mol%.

The developer can be used as a concentrated solution to reduce transportation costs and storage space. When a concentrated solution is used, the concentration is preferably 3 times or less, more preferably 2 times or less, for the purpose of preventing precipitation of the developer components at low temperatures. In addition, components having different solubilities may be stored in several parts, and mixed and diluted at the time of use. The receiving container 20 ° C. At this time, the oxygen permeability at 65% RH is 50ml / m ² atm day or less, usually 1.0~50ml / m ² at
Those made of m day material are preferred.

The developer can be supplied as a solid chemical, that is, a powder.

The replenishing amount of the developing solution is 25 ml or more and 250 ml or less, preferably 30 ml or more and 230 ml or less per 1 m ² of the photosensitive material as a diluted developing solution (ie, used solution).
More preferably, it is 50 ml or more and 200 ml or less.

The development processing temperature and development processing time in the development processing are respectively 20 ° C. to 50 ° C. and 5 to 60 seconds.
It is preferably 8 to 45 seconds at 25 ° C to 40 ° C, more preferably 10 to 30 seconds at 32 ° C to 38 ° C.

In the present invention, the silver halide photographic light-sensitive material is processed according to the processing steps of development, fixing, washing with water (including stabilization), and drying, and the total processing time (Dry to Dry) is from 20 seconds to 100 seconds. Preferably, it is seconds.

The silver halide photographic light-sensitive material is processed using an automatic developing processor (automatic developing machine). The opening ratio of the developing tank is 0.04 cm ^-1 or less, usually 0.01 to 0.04.
It is preferably cm ⁻¹ . Further, each replenisher of the developing solution and the fixing solution is preferably supplied by a mixed dilution method immediately before being supplied from each of these concentrated solutions diluted with water in each of the tanks to be used, and each of the concentrated solutions is It is also preferred that it consists of one part. Further, it is preferable that the containers for the concentrated developing solution and the concentrated fixing solution are an integrated packaging material.

When a chemical mixer is incorporated in the automatic developing apparatus, it is preferable to have a mechanism in which the cartridges for the developing solution and the fixing solution can be used simultaneously.

As the automatic developing device, it is preferable to use an automatic developing machine provided with a rinsing tank and a rinsing roller (crossover roller) between the developing tank and the fixing tank and between the fixing tank and the washing tank. Further, it is preferable that a stock tank for water to be supplied with various water rust preventive agents (antibacterial agents) is installed in the washing tank and the rinsing tank. Further, it is preferable that an electromagnetic valve is installed at the drain of the washing tank.

Further, it is preferable that the rinsing tank of the automatic developing apparatus is a multi-chamber tank or that a multi-stage countercurrent rinsing system is adopted.

Further, it is preferable to provide a roller section in contact with the photosensitive material at a stage preceding the drying section of the automatic developing apparatus.
As described above, the temperature is more preferably set to 70 to 110 ° C.
Further, drying by an infrared radiation method using an infrared radiation object is also preferable. Further, a drying method based on a combination of these is also preferable. The drying time is preferably from 3 seconds to 30 seconds.

In some cases, it is more preferable that the washing water to be used is subjected to a filter member or a filter of activated carbon to remove dust and organic substances present in the water as a pretreatment before being supplied to the washing tank.

Japanese Patent Application Laid-Open No.
Ultraviolet irradiation method described in No. 0-263939, ibid.
No. 263940, using a magnetic field;
No. 131632, a method of making pure water using an ion exchange resin, Japanese Patent Application Nos. 2-2088638 and 2-3.
No. 03055, a method of circulating through a filter and an adsorbent column while blowing ozone, Japanese Patent Application No. Hei.
No. 4,138,164, JP-A-62-115154, JP-A-62-139552 and JP-A-6-153952.
The method using a germicide described in 2-220951 and 62-209532 can be used in combination.

Further, MWBeach, "Microbiological G
rowths in Motion-picture Processing "SMPTE Journal
Vol.85 (1976), RODeegan, "Photo Processing Wash Wa
terBiocides "J. Imaging Tech., Vol. 10, No. 6 (1984) and JP-A-57-8542 and JP-A-57-58143.
58-105145, 57-132146, 58-18631, 57-97530, 57-
Antibacterial agents, antibacterial agents, surfactants and the like described in US Pat. No. 257244 can be used in combination, if necessary.

Further, a washing bath (or a stabilizing bath) may be used, if necessary, by RTKreiman, J. Image, Tech., Vo.
l.10 No.6, page 242 (1984), isothiazoline compounds, bromochlorodimethylhydantoin, Resear
ch Disclosure Volume 205, No. 20526 (May, 1981), Volume 228, No. 22845 (April, 1983, April), isothiazoline compounds described in JP-A-62-209532 Compounds, etc., as antibacterial agent (Microbiocide),
They can be used together if necessary.

In addition, Hiroshi Horiguchi, "Chemistry of Bacterial Prevention and Protection",
Compounds such as those described in Mitsui Shuppan (Showa 57), “Handbook of Bacterial Prevention and Prevention Technology”, Hakuhodo (Showa 61), Japan Society of Bacterial Prevention and Prevention may be included.

The replenishing amount of the washing water and / or the stabilizing solution is preferably 10 liters or less per 1 m ² of the light-sensitive material. The preferred replenishment rate is 100 for a one-stage tank
A 0~5000ml / m ^2, in the case of countercurrent replenishment at two stages to four-stage tank is 50~500ml / m ^2.

The conditions of the washing and stabilizing treatments are preferably 10 to 35 ° C. and 3 to 30 seconds.

There are no particular restrictions on the various additives and the like used in the photographic light-sensitive material of the present invention, other than those described above. For example, those described in the following applicable places can be used. Item 1) Silver halide emulsion and its production method from the lower right column on page 8 of JP-A-2-68539, from line 6 to the upper right column, line 12 on page 10 and page 3-2, 4537 From page 2, lower right column, line 10 to page 1, upper right column, line 1, page 10, upper left column, line 16 to page 11, lower left column, line 19, Japanese Patent Application No. 2-225637. 2) Chemical sensitization method JP-A-2-68539, page 10, line 13, upper right column to line 16, upper left column, Japanese Patent Application No. 3-105035. 3) Color tone improver JP-A-62-276439, page 2, lower left column, line 7 to page 10, lower left column, line 20; JP-A-3-94249, page 6, lower left column, line 15 to line 1 19th line, top right column on page 1. 4) Surfactant, JP-A-2-68539, page 11, upper left column, line 14 antistatic agent to line 12, page 12, upper left column, line 9. 5) Matting agent, slip agent, JP-A-2-68539, page 12, upper left column, 10 plasticizer line, from line 10 to line 10, upper right column, page 14, line 10, lower left column, line 10 to line 1, lower right column . 6) Hydrophilic colloids JP-A-2-68539, page 12, upper right column, line 11 to lower left column, line 16; 7) Hardener From page 17, upper right column, line 17 to page 13, upper right column, line 6 of JP-A-2-68539. 8) Support: Lines 7 to 20 in the upper right column on page 13 of JP-A-2-68539. 9) Crossover JP-A-2-264944, page 4, upper right column, 20 cut method From the line, page 14 upper right column. 10) Dyes and mordants JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9. JP-A-3-24539, page 14, lower left column to page 16, lower right column. 11) Polyhydroxyl JP-A-3-39948, from page 11, upper left column to benzenes, page 12, lower left column, EP Patent No. 452772A. 12) Layer structure JP-A-3-19841. 13) Developing method JP-A-2-103737, page 16, upper right column, line 7 to page 19, lower left column, line 15; and JP-A 2-115837, page 3, lower right column, line 5 Page 6, upper right column, line 10.

[0087]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Example 1 Preparation of (100) AgCl Tabular Emulsion A 1582 ml aqueous gelatin solution (gelatin-1) was placed in a reaction vessel.
(19.5 g of deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g), 1N HNO ₃ solution 7.
8 ml, pH 4.3), NaCl-1 solution (100 ml
13 ml of NaCl (containing 10 g of NaCl therein),
While maintaining the temperature at 0 ° C., Ag-1 (AgNO _{3 in} 100 ml) was used.
20 g) and solution X-1 (NaCl in 100 ml).
7.05 g) at 62.4 ml / min. In 15.6 ml portions. After stirring for 3 minutes, the Ag-2 solution (1
100 ml of AgNO _{3 in} 2 ml) and X-2 solution (100
(containing 1.4 g of KBr in ml) at 80.6 ml / min.
8.2 ml was mixed simultaneously. After stirring for 3 minutes, Ag-
Solution 1 and solution X-1 were simultaneously mixed and added at a rate of 62.4 ml / min in 46.8 ml portions. After stirring for 2 minutes, aqueous gelatin solution 20
3 ml (oxidized gelatin-11.3 g, NaCl 1.
3 g, containing a 1N NaOH solution to adjust the pH to 5.5), and the pCl was adjusted to 1.8.
The temperature was raised to 1.8 and the mixture was aged for 10 minutes.
Thereafter, a disulfide compound A (described below) was added in an amount of 1 × 10 ⁻⁴ mol per mol of silver halide, and an AgCl fine grain emulsion (average grain diameter: 0.1 μm) was added at 2.68 × 10 4
^The addition was carried out for 20 minutes at an AgCl addition rate of ^-2 mol / min. After aging for 10 minutes after the addition, a precipitant was added, and the temperature was increased to 35 ° C.
And washed down. Add gelatin aqueous solution, 60 ℃
Was adjusted to pH 6.0.

[0088]

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A transmission electron micrograph (hereinafter referred to as TEM) of a replica of the particles was observed. The resulting emulsion was high silver chloride (100) tabular grains containing 0.44 mol% of AgBr based on silver. The shape characteristic values of the particles were as follows. (Total projected area of tabular grains having an aspect ratio of 5 or more / total A)
gX grain projected area sum) × 100 = a ₁ = 90% (average aspect ratio of tabular grains (average diameter / average thickness)) = a ₂ = 9.3 (average diameter of tabular grains) = a ₃ = 1.67 μm (average thickness) = a ₄ = 0.18 μm

Chemical sensitization Chemical sensitization was performed while maintaining the particles prepared as described above at 60 ° C. while stirring. First, 10 ^-4 mol of thiosulfonic acid compound-I was added per 1 mol of silver halide,
Then added 1.0 mol% of AgBr particles having a diameter of 0.10μm against total silver, of 1% KI solution after 5 minutes per mol of silver halide 10 ^-3 mol was added, and after another 3 minutes ,
1 × 10 ⁻⁶ mol / mol Ag was added to thiourea dioxide, and 2
Reduction sensitization was performed by holding for 2 minutes. Next, 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was added to 3 × 10 ⁻⁴ mol / mol Ag and sensitizing dye I-1.
0 (Table 1) was added in an amount of 0.7 × 10 ⁻³ mol per mol of silver halide as an amount of the sensitizing dye I-10. Sample A using sensitizing dye I-10 was used. For comparison, a sample using the same amount of the comparative sensitizing dye-1 was used as a sample B, and a sample using the same amount of the comparative sensitizing dye-2 was used as a sample C.
And Dispersions of these comparative dyes were prepared in the same manner as Dye I-10, and used as dispersions. The thiosulfonic acid compound-I and dyes-1 and -2 used above are shown below.

[0091]

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The dispersion of sensitizing dye I-10 was prepared as follows.

(Preparation of Dispersion of Sensitizing Dye I-10) Water 5
For 0 ml, 1 g of sensitizing dye I-10 was added at pH 7.0 ±.
0.5, 50-65 ° C, 20
The particles were mechanically dispersed in solid fine particles of 1 μm or less at 00 to 2500 rpm, 50 g of 10% gelatin was added, mixed, and cooled. Further, chloroauric acid (3 × 10 ⁻⁶ mol / mol silver) and potassium thiocyanate (1.8 × 10 ⁻³ mol / mol silver) were added, and after 5 minutes, sodium thiosulfate (4.6 × 10 ⁻⁶ mol / mol silver).
10 ⁻⁶ mol / mol silver) and selenium compound-1 (1.2 × 1)
0 ^-6 mol / mol silver) and tellurium compound-2 (3.6 × 10
^-6 mol / mole silver). After 5 minutes, the nucleic acid (67 mg /
Mol silver) and mercapto compound-3 (3 × 10 ^−5).
Mol / mole silver) was added. 30 minutes later, water-soluble mercapto compound-4 (1 × 10 ⁻⁴ mol / mol silver) was added, and 35
Cooled to ° C. Compounds 1 to 4 in the above are shown below.

[0094]

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[0095]

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(Preparation of Emulsion Coating Solution) The following chemicals were added per mole of silver halide to the chemically sensitized emulsion to prepare an emulsion coating solution. 80.6 g of gelatin (including gelatin in the emulsion) 21.5 g of dextran (average molecular weight 39,000) 5.1 g of sodium polyacrylate (average molecular weight 400,000) 5.1 g of sodium polystyrene sulfonate (average molecular weight 60) 1.2 g-Potassium iodide-78 mg-Hardener 1,2-bis (vinylsulfonylacetamido) ethane (adjusted so that the swelling ratio determined as described below is 140%)

Further, the following compounds I to VIII were added in the following amounts. Compound-I 70 mg Compound-II 5.0 g Compound-III 0.58 g Compound-IV 30 mg Compound-V 0.16 g Compound-VI 6.0 mg Compound-VII 0.1 g Compound-VIII 0.1 g Compound-I to VIII It is shown below.

[0098]

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[0099]

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The following polymer latex having an active methylene group was added in an adjusted amount so as to give a coating amount of 0.8 g / m ² . Polymer latex Core / shell latex Core: shell = 50: 50 (weight percentage) Core: styrene / butadiene copolymer (37/63 weight percentage) Shell: styrene / 2-acetoacetoxyethyl methacrylate (84/16 weight percentage) Average Particle size: about 0.1 μm (adjusted to pH 6.1 with NaOH) Dye emulsion a was added to the above coating solution such that the following dye-I was applied in an amount of 10 mg / m ² per one side.

(Preparation of dye emulsion a) The following dye-I6
0 g, 2,2.8 g of 2,4-diaminophenol, 62.8 g of dicyclohexyl phthalate and 33 of ethyl acetate
3 g were melted at 60 ° C. Next, 65 ml of a 5% aqueous solution of sodium dodecylbenzenesulfonate and gelatin 94
g and water (581 ml) were added and the mixture was dissolved at 60 ° C.
Emulsified and dispersed for 0 minutes. Next, 2 g of methyl p-hydroxybenzoate and 6 liters of water were added, and the temperature was lowered to 40 ° C. Next, Asahi Kasei ultrafiltration lab module ACP10
Using 50, the mixture was concentrated until the total amount became 2 kg, and 1 g of methyl p-hydroxybenzoate was added to obtain a dye emulsion a.

[0102]

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(Preparation of Dye Layer Coating Solution) A coating solution was prepared so that each component of the dye layer to be coated as the lower layer of the emulsion had the following coating amount.・ Gelatin 0.25 g / m ²・ Additive D (described below) 1.4 mg / m ²・ Sodium polystyrene sulfonate (average molecular weight: 600,000) 5.9 mg / m ²・ Dye dispersion i (as dye solid content) 20 mg / M ² dye dispersion i was prepared as follows.

(Preparation of Dye Dispersion i) The following Dye-II was treated as a wet cake without drying, and weighed to a dry solid content of 6.3 g. The following Dispersing Aid V was treated as a 25% by weight aqueous solution, and was added so that the dry solid content was 30% by weight based on the dye solid content. Water was added to make a total amount of 63.3 g, and mixed well to form a slurry. 100 zirconia beads with an average diameter of 0.5 mm
ml, put it in a vessel together with the slurry, disperse it in a disperser (1 / 16G sand grinder mill: manufactured by Imex Co., Ltd.) for 6 hours, and add water so that the dye concentration becomes 8% by weight. I got The resulting dispersant is
A dye solid content of 5% by weight and a photographic gelatin were mixed so as to be equal to the weight of the dye solid content, and an aqueous solution was added as a preservative so that the following additive D was 2,000 ppm based on the gelatin, and refrigerated. And stored in jelly form. Thus, a dye dispersion i was obtained as a non-elutable solid fine particle dispersion dye having a light absorption maximum at 915 nm. The average particle diameter of the solid fine particles of the dye dispersion i was 0.4 μm.

[0105]

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[0106]

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(Preparation of Coating Solution for Surface Protective Layer) A coating solution for the surface protective layer was prepared such that each component of the surface protective layer was coated as follows on one side of the support.・ Gelatin 0.65 mg / m ²・ Additive D 1.4 mg / m ²・ Sodium polyacrylate (average molecular weight 41,000) 34 mg / m ²・ Additive-1 40 mg / m ²・ Additive-25 .4mg / m ² · additives -3 22.5mg / m ² · additives -4 0.5mg / m ² · matting agent-1 (average particle size 3.7μm) 72.5mg / m ² · compound -IX 4.4 mg / m ² · Compound-X 1.3 mg / m ² Additives and the like used in the above are as follows.

[0108]

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[0109]

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(Preparation of Support) Biaxially stretched thickness 17
Corona discharge treatment was performed on a 5 μm blue dyed polyethylene terephthalate film, and both surfaces were coated with a wire bar coater so that the hydrophobic polymer layer had the following coating amount, and dried at 185 ° C. for 1 minute.

[0111] (hydrophobic polymer layer) Butadiene - Styrene copolymer latex of butadiene / styrene weight ratio ^{= 31/69 0.32g / m 2} · 2,4- dichloro-6-hydroxy -s- triazine sodium salt 8. In the 4 mg / m ² * latex solution, the following emulsifying dispersant-A was added in an amount of 0. Contains 4wt%.

[0112]

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Next, the hydrophilic colloid layer was coated on both sides with a wire bar coater so that the following coating amount was obtained.
Dry at 5 ° C. for 1 minute.

(Hydrophilic colloid layer) ・ Gelatin 80 mg / m ²・ Polyethyl acrylate 20 mg / m ²・ Coating aid-B 1.8 mg / m ²・ Dye-III 40 mg / m ²・ Additive D 0.27 mg / M ²

Method for Preparing Dye-III 20 g of the following Dye-III, 200 g of a 1% aqueous solution of carboxymethylcellulose and 287 g of H ₂ O were mixed, and Eiger Mill (Eiger Japan) was used using zirconium oxide (ZrO ₂ ) beads having a diameter of 2 mm. 5,0)
The treatment was performed at 00 rpm for 8 hours. The resulting mixture was filtered to remove ZrO ₂ beads. This was dispersed in an aqueous gelatin solution to obtain a dye dispersion in the form of solid fine particles of Dye-III. The dye concentration was 12% by weight, and the average solid particle diameter of the dye was 0.37 μm. The compounds used in the above are shown below.

[0116]

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(Preparation of photosensitive material) The above emulsion layer and surface protective layer were combined on the support prepared as described above and coated on a screen by a simultaneous extrusion method. The amount of silver coated on one side was 1.3 g / m ² . Thus, the photosensitive material A,
B and C were obtained.

The swelling ratio is determined as follows.

Measurement of swelling ratio First, the photographic material to be measured was aged at 40 ° C. and 60% RH for 7 days. Next, this photosensitive material was immersed in distilled water at 21 ° C. for 3 minutes, and this state was frozen and fixed with liquid nitrogen. After cutting this photosensitive material with a microtome so as to be perpendicular to the photosensitive material surface,
Lyophilized at -90 ° C. The treated product was observed with a scanning electron microscope to determine the swollen film thickness Tw. On the other hand, the film thickness Td in a dry state was also determined by cross-sectional observation using a scanning electron microscope. The value obtained by dividing the difference between Tw and Td thus obtained by Td and multiplying by 100 was defined as the swelling ratio (unit%).

(Preparation of development replenisher) A developer having the following formulation and using sodium erythorbate as a developing agent was prepared. Diethylenetriaminepentaacetic acid 4.0 g Potassium carbonate 62.9 g Sodium bicarbonate 20.6 g Sodium sulfite 15.0 g Sodium erythorbate 35.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 2.0 g Potassium bromide 4.0 g diethylene glycol 25.0 g 2,5-dimercapto-1,3,4-thiadiazole 0.1 g 3,3'-dithiobishydrocinnamic acid 0.5 g Water is added (pH = 9.90) 500 ml 500 ml of water is added to 500 ml of the above concentrated solution to make 1 liter of a developing replenisher. By adding 10.0 g of acetic acid per liter of the above developing replenisher, pH =
9.5 is used as a developing mother liquor.

(Preparation of Fixing Solution) Ethylenediaminetetraacetic acid disodium 0.05 g Sodium thiosulfate pentahydrate 220.0 g Sodium sulfite 3.0 g As shown in Tables 2 and 3, each organic acid was added at each concentration. To 1 liter and adjust to pH 4.90 with NaOH. The fixer is the same as that described above for both the mother liquor and the replenisher.

(Washing water replenisher) Diethylenetriaminepentaacetic acid 0.5 g Sodium sulfite 1.0 g 5-sulfosalicylic acid 0.6 g Distilled water is added, and the pH is adjusted to pH 5.5 with 1 liter of NaOH.

(Processing Process of Photosensitive Material) CEPROS-S manufactured by Fuji Photo Film Co., Ltd. was modified, and the washing tank was replaced with two-stage countercurrent washing, and the second washing layer was supplemented with washing water. The opening ratios of the developing tank and the fixing tank were improved to 0.02 cm ^-1 . The capacity of each washing tank is 6 liters. Drying is performed by a heat roller method (roller surface temperature 8
5 ° C.) and an infrared radiation system, and a heat roller was provided upstream of the drying unit. Using the developing mother liquor, the fixing mother liquor and the rinsing water replenisher, the developing replenisher, the fixing replenisher and the rinsing water replenisher were all added at 100 per m ^{2 of the} light-sensitive material.
Treatment with replenishing ml (invention), or 30
The experiment was performed by a method of treating while supplementing 0 ml (Comparative Example). Process temperature Processing time Current image 35 ° C 16 seconds Fixed 35 ° C 14 seconds Rinse 1st 30 ° C 10 seconds Rinse 2nd 25 ° C 10 seconds Dry 6 seconds Total 56 seconds 4m ² of photosensitive material per day The running process was performed for 2 months while processing.

In the above experiments, the solubility of each organic acid in the fixing solution used, rust of metal, drying property and residual color were examined as follows.

(Solubility of Organic Acids)
When the concentration was 3 times the concentration of the working solution shown in the above, the sample which could be dissolved was marked with “○”, and the insoluble one was marked with “×”. Insoluble materials were not tested for "rust of metal", "dryness", and "residual color".

(Metal rust) 10 ml of each fixing solution was added to 2
Seal in a 00 ml glass bottle, put metal in this
After 1 week, the state where the used metal surface was very rusted was evaluated as “1”, and the state where almost no rust was generated was evaluated as “5”, and relatively evaluated on a five-point scale. “4” is a practically acceptable level. In the case of "3" or less, it is out of tolerance, and it is necessary to provide a function of exhausting gas generated from the automatic developing machine to be used outside the room.

(Evaluation of Drying Property of Film Sensitive Material) The film surface when coming out of the drying step of the automatic developing machine under the above-mentioned processing conditions was evaluated by the following evaluation by touch. The evaluation was performed two months after the fixing solution during the running process was sufficiently equilibrated. "5": The film feels warm even when touching the surface of the film, and the film is sufficiently dried. "4": Touching the surface of the film does not give any warmth, but the film is dry. "3": Some moisture remains on the surface of the film, and when the film is overlaid, the film adheres to the film and is unacceptably practical for drying. "2": A film with much moisture remaining on the surface of the film, worse than the condition of "3". "1": Worse than the state of "2".

(Evaluation of residual color) Each photosensitive material was 30.5 cm ×
After cutting to 25.4 cm, the washing water was treated at 5 ° C., and the degree of residual color of each photosensitive material was visually evaluated according to the following criteria. A: Almost no residual color. …: The color remains slightly, but it does not matter. Δ: Remaining color but practically acceptable. ×: Many residual colors are not possible. Tables 2 and 3 show these results.

[0129]

[Table 2]

[0130]

[Table 3]

As shown in the results of Tables 2 and 3, the samples without organic acid (Experiment Nos. 1, 2 and 3) did not generate metal rust, but the film had remarkably poor drying properties. In particular, photosensitive material B,
In the case of C (Experiment Nos. 2 and 3), the residual color was also poor. When acetic acid, which is usually used in a fixing solution, is used at a high concentration, the drying property is improved, but metal rust is remarkably generated (Experiment Nos. 7, 8, and 9). As shown in Table 2, citric acid, tartaric acid, malonic acid, and the like, which cannot replace acetic acid, can be dissolved at a high concentration. For maleic acid, 0.2
Even when the amount is set to mol / liter, the drying property under low replenishment conditions is not sufficient even when combined with photosensitive material A. On the other hand, when the amount of succinic acid is 0.15 mol / L or more within the range of the present invention, good drying properties can be obtained without any problem with respect to metal rust. In particular, in the case of Experiment No. 23 using the photosensitive material A, a good result of residual color can be obtained.

[0132]

According to the present invention, even under low replenishment conditions, the photosensitive material has good drying properties, has no residual color, and is free from rust on metal parts of an automatic developing apparatus having no exhaust means. Disappears.

Claims (3)

[Claims] 1. A method for developing, fixing, washing and drying a silver halide photographic material having at least one silver halide emulsion layer on a support using an automatic developing machine. In the processing method, at least one kind of a benzimidazolocarbocyanine dye represented by the general formula (I) is adsorbed on the silver halide grains contained in the silver halide emulsion layer, and at least 0.15 mol / m A method for processing a silver halide photographic material, wherein the processing is performed with a fixing solution containing 1 liter of succinic acid. Embedded image [In the general formula (I), R ₁₁ and R ₁₂ each represent an alkyl group, and at least one of R ₁₁ and R ₁₂ represents an alkoxyalkyl group. R ₁₃ and R ₁₄ each represent an alkyl group, and at least one of R ₁₃ and R ₁₄ represents a sulfoalkyl group. X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ are each the same,
Or may be different, and represents a hydrogen atom, a cyano group, a halogen-substituted alkyl group, or a halogen atom, and at least one of X ₁₁ and X ₁₃ represents a hydrogen atom. Z represents an ion necessary to balance the charge, and n ₁ is 1 or 2, and 1 when an internal salt is formed. ] 2. One meter of a silver halide photographic light-sensitive material of a fixing solution
^{2. The method} for processing a silver halide photographic light-sensitive material according to claim 1, wherein the processing is carried out with a replenishing amount per 250 ml or less. 3. An average aspect ratio of at least 70% of the total projected area of silver halide grains of a silver halide photographic light-sensitive material.
3. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein said number is less than 20.