JPH09114065A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce the amt. of a processing soln. to be replenished, to shorten desilvering time and to enable continuous processing even during inactive processing by processing a sensitive material contg. flat platy particles having a specified silver chloride content with a processing soln. contg. a specified metallic chelate compd. and having bleaching ability after color development. SOLUTION: A sensitive material contg. flat platy silver halide particles having (100) faces as principal planes and >=50mol% silver chloride content in an emulsion layer is processed with a processing soln. contg. a metallic chelate compd. represented by the formula and having bleaching ability after color development. In the formula, R1 is aliphatic hydrocarbon, aryl, etc., R2 is H, aliphatic hydrocarbon, etc., each of L1 -L5 is alkylene, each of (m) and (n) is 0 or 1, each of W<1> and W<2> is alkylene, arylene, etc., D is a single bond, -O-, -N(Rw)-, etc., Rw is H, aliphatic hydrocarbon, etc., (v) is an integer of 0-3, (w) is an integer of 1-3 and each of M1 -M4 is H or a cation.

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 color photographic light-sensitive material (hereinafter sometimes simply referred to as a light-sensitive material), and more specifically, improvement of desilvering property and / or processing. The present invention relates to a subsequent processing method excellent in image storability, and can shorten the processing time.

[0002]

2. Description of the Related Art At present, the most popular image recording method is the negative / paper method, in which a color negative film is loaded into a camera, photographed, developed and printed on a color photographic paper (also called color paper). It is a method of developing to obtain a color image (also referred to as a print). The printing and developing processes in this method are outsourced to specialized developing laboratories called laboratories through a handling shop, but the quality and speed of the processing system are not enough to satisfy the user's requirements. Not not. The user's dissatisfaction is, for example: 1. Insufficient adjustment of print finish color and density; 2. Reprinted print is different from previous print; 3.
To get a print from a development request, you must go to the store twice; and so on.

The problems of quality 1 and 2 can be solved by providing the negative film with information on the user's photographing and information on the previous printing. As a specific proposal thereof, in International Publication WO90 / 04205, a back surface of a film (a side not coated with a silver halide emulsion layer) is coated with a light-transmitting magnetic recording layer, and a film manufacturer It has been proposed to provide information recording areas for camera users, labs and dealers as separate tracks.

The problem concerning the speediness of 3 is "CN-16.
L / CP-47L ”and other color processing agents for rapid use and minilabs have spread to speed up the processing system and enable finishing on the day. However, it takes about 20 minutes to get a print from the development request. The fact is that we have to wait a minimum and go to the shops twice, so further speeding up of processing is a very important issue. The possibility of processing has reached its limit, and in order to further speed up processing, it is essential to develop a photosensitive material adapted for rapid processing.

Increasing the silver chloride content of the silver halide emulsion increases the water solubility, achieves development and fixing in a shorter time, and provides a silver halide emulsion suitable for rapid processing. So-called tabular grains having a grain size considerably larger than the grain thickness are preferred in order to enhance the sensitivity of the photographic silver halide emulsion and to enhance sharpness, graininess, color sensitization efficiency with a sensitizing dye, and covering power. This is well known to those skilled in the art. Generally, silver halide grains having a high silver chloride content (hereinafter sometimes simply referred to as high silver chloride grains) are likely to be cubic grains, and tabular grains are
Some ingenuity is required, and tabular silver halide grains having a high silver chloride content on the (111) major surface (hereinafter sometimes simply referred to as high silver chloride tabular grains) do not have high stability. However, it has a drawback that the tabular shape of grains may be collapsed during emulsion production. U.S. Pat. No. 5,264,337 describes a method for solving the above drawbacks of high silver chloride tabular grains and a method for producing high silver chloride tabular grains having a (100) major surface. In addition, as a means for achieving rapid desilvering, (10
0) Sensitive material containing high-silver chloride tabular grains on the main surface and 1,3
-Treatment method containing diaminopropane tetraacetic acid ferric iron complex salt and / or dicarboxylic acid compound is disclosed in JP-A-7-1816.
No. 53.

The inventor of the present invention has disclosed in Japanese Unexamined Patent Publication No.
As a result of applying the processing method described in -181653, the desired desilvering performance was obtained. However, it is clear that if a continuous automatization process is performed for a long period of time, it will cause a new problem that periodic maintenance is required due to clogging of the circulation system filter and stains on the photosensitive material. Became. This tendency is due to low replenishment of the color developing solution,
It was found that when the amount of elution from the light-sensitive material increased, and the amount of oxidative decomposition products in the color developing solution increased due to the quiet processing, it markedly appeared. As described above, the conventionally known photosensitive materials and processing methods have various problems, and it is necessary to develop a further processing method.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to reduce the total replenishment amount of a processing solution (especially bleach-fixing solution) and shorten the processing time (especially desilvering time) in a quiet process. Another object is to provide a treatment method that enables stable continuous treatment for a long period of time.

[0008]

The above objects have been achieved by the following processing methods. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, and a flat plate having a silver chloride content of 50 mol% or more having (100) plane as a main plane in the emulsion layer of the light-sensitive material. At least one kind of metal chelate compound of the compound represented by the general formula (I) A method of processing a silver halide color photographic light-sensitive material, which comprises processing with a processing solution containing bleaching ability. General formula (I)

[0009]

Embedded image

(In the formula, R ₁ represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. R ₂ represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group.
₁ , L ₂ , L ₃ , L ₄ and L ₅ each represent an alkylene group. m and n each represent 0 or 1. W ¹ and W ² each represent an alkylene group, an arylene group, an aralkylene group or a divalent nitrogen-containing heterocyclic group. D is a single bond, -O-, -S- or -N (R
w) -represents. Rw represents a hydrogen atom, an aliphatic hydrocarbon group or an aryl group. v represents an integer of 0 to 3, w is 1
Represents an integer of 3; M ₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation. )

The structural characteristic of the general formula (I) is that a branched alkylene group is introduced between the carboxyl group and N of the aminopolycarboxylic acid. So far, a branched alkylene chain between N and N'has been disclosed (JP-A-3-192254, etc.), but this compound has not been able to solve the above-mentioned problems, and a carboxyl group and N It is unpredictable that the problem could be solved by introducing a branched alkylene group into a specific site called "ma".

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
First, the high silver chloride tabular grains used in the present invention will be described.

Tabular silver halide grains having a (100) plane as a main plane and a silver chloride content of 50 mol% or more used in the present invention (hereinafter sometimes referred to as tabular grains).
The silver chloride content of is preferably 75 mol% or more, more preferably 90 mol% or more, and most preferably 9 mol% or more.
It is 5 mol% or more.

The silver halide emulsion used in the present invention is a silver halide emulsion containing at least a dispersion medium and the above-mentioned silver halide grains, and 10% of the total projected area of all the silver halide grains in the emulsion. Or more, preferably 35 to 100
%, And more preferably 60 to 100% is (10
It is a tabular silver halide grain having a (0) plane. The term "projected area" as used herein means the projected area of silver halide emulsion grains when they are arranged on a substrate in a state where they do not overlap each other and tabular grains are arranged such that the principal planes thereof are parallel to the substrate surface. In addition, the main plane refers to two parallel maximum outer surfaces in one tabular grain. The aspect ratio (diameter / thickness) of the tabular grains is 1.5 or more, preferably 2 or more,
It is more preferably 3 to 25, still more preferably 3 to 15. Here, the diameter means that when the particles are observed with an electron microscope,
It refers to the diameter of a circle having an area equal to the projected area of the grain. The thickness means the distance between the main planes of tabular grains. The diameter of the tabular silver halide grains is preferably 10 μm or less, more preferably 0.2 to 5 μm, and 0.2
˜3 μm is more preferred. Further, the thickness is preferably 0.7 μm or less, more preferably 0.03 to 0.3 μm, and 0.
05-0.2 μm is more preferable. The particle size distribution of the tabular grains is preferably monodisperse, and the coefficient of variation is preferably 40% or less, more preferably 20% or less.

The "principal plane" is defined as a set of parallel planes having the largest area among the crystal surfaces forming substantially rectangular parallelepiped emulsion grains, and the fact that the principal plane is the (100) plane is determined by electron beam diffraction. Method or X-ray diffraction method. A substantially rectangular parallelepiped emulsion grain means that the main plane is (100)
Although it is formed from a plane, it may have {111} crystal faces from 1 to 8. That is, a rectangular parallelepiped 8
One to eight of the four corners may have a sharpened shape.

The two parallel principal planes used in the present invention are (100) planes, and the silver chloride content of the grains is 50 mol%.
Emulsions containing high silver chloride tabular grains as described above are disclosed in European Patent No. 0,534,395A1 and US Pat. No. 5,264,337, or Japanese Patent Application No. 5-96250.
It can be prepared according to the method described below in No. From the viewpoint of production stability and monodispersity of particle size, the method described in Japanese Patent Application No. 5-96250 is preferable.

1) Nucleation process The tabular nuclei, which are the nuclei of tabular grains, have a high production ratio under the condition that the introduction of lattice defects easily occurs. As a method for obtaining plate nuclei with high reproducibility and a high production ratio, a method utilizing halogen conversion of product nuclei is effective. In this method, first, silver halide nucleation is performed, and subsequently, a halogen ion which forms a more sparingly soluble silver halide is introduced to perform halogen conversion. More specifically, the halogen composition structure of the nucleus formed during nucleation has, for example, a structure of (AgX ₁ | AgX ₂ ) or (AgX ₁ | AgX ₄ | AgX ₃ ). This structure can be formed by, for example, simultaneously mixing and adding an aqueous silver salt solution and an aqueous halide salt solution to discontinuously change the halogen composition of the aqueous halide solution.
Alternatively, a halide salt aqueous solution is added to the dispersion medium solution, and then a silver salt aqueous solution is added to form AgX ₁ , then another halide salt aqueous solution is added, and then a silver salt aqueous solution is added, ( An AgX ₁ | AgX ₂ ) structure can be prepared, or a combination thereof can be prepared.

AgX ₁ and AgX ₂ and AgX ₁ and Ag
X ₄ , AgX ₄ and AgX ₃ have a Cl ⁻ content or Br ⁻
The contents differ by 25-100 mol%, preferably by 50-100 mol%, more preferably by 75-100 mol%.
Further, in addition to the difference in Cl ^- content or Br ^- content, or the I ^- content is 5 to 100 mol%, preferably 10 to 100.
They differ by mol%, more preferably 30-100 mol%. In addition, there can be mentioned an embodiment in which the Cl ^- content difference or the Br ^- content difference complies with the above-mentioned rules, and the I ^- content difference is 0 to 5 mol%. The molar ratio of AgX ₁ : AgX _{2 in} the case of (AgX ₁ | AgX ₂ ), and (AgX ₁ | Ag
The molar ratio of AgX ₁ : AgX ₂ : AgX _{3 in} (X ₄ | AgX ₃ ) can be variously changed, and the molar ratio that provides the most preferable embodiment of the present invention can be selected and used.

The grain equivalent to the circle, which is the core of the tabular grains, has a projected grain diameter of preferably 0.15 μm or less,
0.1 μm is more preferable, and 0.01 to 0.1 μm is still more preferable.

The concentration of the dispersion medium in the dispersion medium solution during nucleation is 0.
01 to 10% by weight is preferable, and 0.02 to 5% by weight is more preferable. 1-10 are preferable and, as for pH, 2-9 are more preferable. The temperature is preferably 10 to 80 ° C, and 30 to 60
C is more preferred. The excess Br ^- concentration is preferably 10 ^-2 mol / l or less, more preferably 10 ^-2.5 mol / l or less. Excess Cl ^- concentration is pCl = 0.8-3.0
Is preferred, and 1.2 to 2.8 is more preferred.

At the time of nucleation, a dispersion medium can be added to the silver salt aqueous solution and / or the halide salt aqueous solution added to enable uniform nucleation. The dispersion medium concentration is preferably 0.01% by weight or more, more preferably 0.02 to 2% by weight, still more preferably 0.05 to 1% by weight. A low molecular weight gelatin having a molecular weight of 3,000 to 60,000, preferably 8,000 to 40,000 is more preferable. Furthermore, it is more preferable that the aqueous solution of silver salt and the aqueous solution of halide salt are directly added to the liquid through a porous body addition system having 3 to 10 ¹⁵ , preferably 30 to 10 ¹⁵ pores. For details, see Japanese Patent Laid-Open No. 3-
No. 21339, No. 4-193336, and Japanese Patent Application No. 4-24
The description of No. 0283 can be referred to. As for gelatin, the frequency of formation of the defect is higher in gelatin having a lower methionine content. From the gelatin having a methionine content of 1 to 60 μmol / g, the most preferable gelatin can be selected and used according to each case.

By lowering the concentration of excess halogen ions or the concentration of excess silver ions at the time of nucleation, the mixing ratio of twin grains can be reduced.

A silver salt aqueous solution and a halide salt aqueous solution are added by a simultaneous mixing method to a dispersion medium solution containing at least a dispersion medium and water with stirring to form nuclei. The Cl ⁻ concentration in the dispersion medium solution during nucleation is preferably 10 ^−1.5 mol / liter or less, and the silver ion concentration is preferably 10 ⁻² mol / liter or less. The pH is preferably 2 or more, more preferably 5 to 10. The gelatin concentration is preferably 0.01 to 3% by weight,
0.03 to 2% by weight is more preferable.

The temperature during nucleation is not limited, but usually 1
0 degreeC-80 degreeC is preferable, and 20-70 degreeC is more preferable. The addition rate of the aqueous silver salt solution is preferably 0.3 to 20 g / min, and more preferably 0.5 to 15 g / min, per liter of the container solution. The pH of the container solution is not particularly limited, but usually pH 1 to 11, preferably pH 3 to 10 is used. The most preferable pH value can be selected and used according to the combination of excess silver ion concentration, temperature, and the like.

It is preferable that substantially no NH ₃ coexist in the nucleation process. Here, “substantially” means that the silver halide solvent concentration d ₀ is preferably d ₀ ≦ 0.5 mol / l, more preferably d ₀ <0.1 mol / l, and further preferably d ₀ <0.02. Refers to mole / liter. It is preferable that substantially no silver halide solvent other than NH ₃ is allowed to coexist in the nucleation and growth processes. Here, “substantially” means the same as the d ₁ concentration regulation. As a silver halide solvent other than NH ₃ , thioethers, thioureas,
Examples of the antifoggants include thiocyanates, organic amine compounds, and tetrazaindene compounds, and thioethers, thioureas, and thiocyanates are preferable.

2) Aging Process It is not possible to separately prepare tabular grain nuclei during nucleation. Therefore, tabular grains are grown by Ostwald ripening in the next ripening step, and other grains are extinguished. The aging temperature is 40 ° C or higher, preferably 45 to 90 ° C, more preferably 50 to 80 ° C.

In the present invention, it is preferable that the silver halide solvent is not allowed to substantially coexist during ripening.
Here, “substantially” complies with the above rules.

The pH during aging is 1 to 12, preferably 1.
It is 5-8, more preferably 1.7-6.

As the dispersion medium for nucleation, ripening and growth, a conventionally known dispersion medium for silver halide emulsions can be used, but the methionine content is particularly preferably 0-5.
0 μmol / g, more preferably 0 to 30 μmol / g gelatin can be preferably used. When the gelatin is used during ripening and growth, thinner tabular grains having a uniform diameter size distribution are preferably formed. Also, Japanese Patent Publication No. 52-16365, Journal of the Photographic Society of Japan, 29 (1), 17, 22 (1966), 30 (1),
10, 19 (1967), 30 volumes (2), 17 (1)
967), 33 (3), 24 (1967) can be preferably used as a dispersion medium. Further, a crystal habit controlling agent described in EP 0534395A1 can be used in combination. The dispersion medium concentration is 0.1 to
10% by weight is preferred, and the control agent is preferably from 10 ^-1 to
10 ^-6 mol / l, more preferably 10 ^-2 to 10 ^-5
It can be used in moles / liter. These can be added at any time from before nucleation to the end of growth. It can be added to the existing dispersion medium in the form of additional addition, or can be added after the existing dispersion medium is removed by centrifugation or the like.

3) Growth Process After the tabular grain ratio is increased by aging, a solute is added next to further grow the tabular grains. As the solute addition method, 1) a solution addition method (a method of adding a silver salt aqueous solution and a halide salt aqueous solution), 2) a fine grain emulsion addition method of previously forming fine silver halide grains and adding the fine grains,
3) A method of using both in combination. In order to grow the tabular grains preferentially in the edge direction, it is necessary to grow the tabular grains at a low supersaturation concentration within a range that does not undergo Ostwald ripening. That is, it is necessary to control the concentration at a low supersaturated concentration with high accuracy. 2)
The method (1) is more preferable because it enables this.

In the fine grain emulsion addition method, the diameter is 0.15 μm or less, preferably 0.1 μm or less, more preferably 0.1 μm or less.
A silver halide fine grain emulsion having a grain size of 06 μm or less is added, and tabular grains are grown by Ostwald ripening. The fine grain emulsion can be added continuously or intermittently. The fine particle emulsion can be continuously prepared by supplying an aqueous solution of a silver salt and an aqueous solution of a halide salt in a mixer provided in the vicinity of the reaction vessel, and can be immediately and continuously added to the reaction vessel. And then added continuously or intermittently.
The fine particles preferably do not substantially contain twin particles. The term “substantially free of” means that the twin grain number ratio is 5% or less, preferably 1% or less, more preferably 0.5% or less.

The halogen composition of the fine grains may be silver chloride, silver bromide, silver iodide, or a mixed crystal of two or more thereof.

The solution conditions during grain growth are the same as the above-mentioned aging conditions. Both are steps for growing tabular grains by Ostwald ripening and eliminating other fine particles, and are mechanically the same. For details of the method for adding a fine grain emulsion, see Japanese Patent Application No. 2-142635,
The description in JP-A-4-77261 and JP-A-1-183417 can be referred to.

In order to form fine particles having substantially no twin planes, the excess halogen ion concentration or excess silver ion concentration is preferably 10 ^-2 mol / liter or less, and the silver salt aqueous solution and the halide salt aqueous solution are mixed. It may be formed by adding by the simultaneous mixing and adding method.

The fine particle formation temperature is preferably 50 ° C. or lower,
5-40 degreeC is more preferable, and 10-35 degreeC is still more preferable. The dispersion medium preferably has a molecular weight of 2,000 to 6 × 10
⁴ , more preferably 5000 to ⁴ × 10 ⁴ low molecular weight gelatin is preferably 30% by weight or more, more preferably 6% by weight or more.
Gelatin occupying 0% by weight or more, more preferably 80% by weight or more is preferred. The dispersion medium concentration is preferably 0.02% by weight or more, more preferably 0.1 to 5% by weight.

Dislocation lines can be introduced into the grains during the formation of the grains by the halogen composition gap method, the halogen conversion method, the epitaxial growth method and a combination thereof. Pressure fogging characteristics, reciprocity characteristics, and color sensitization characteristics are further improved and are preferable. Regarding this, JP-A-63-2
20238, 64-26839, JP-A-2-1276
35, 3-189644, 3-175440, 2
-123346, European Patent 0460656A1 Journal
of Imaging Science, 32 volumes, 160-177 (19
88) can be referred to.

The obtained particles may be used as host particles to form epitaxial particles. Further, particles having dislocation lines therein may be formed using the particles as a core.
In addition, using the grains as a substrate, a silver halide layer having a different halogen composition from the substrate is laminated,
Particles of any of a variety of known particle structures can be made.

A shallow inner latent emulsion may be formed by using the tabular grains as a core. Also, core / shell type particles can be formed. This is described in
No. 133542, No. 63-151618, U.S. Pat. Nos. 3,206,313, 3,317,322, 3,761,276, 4,269,927, and 3,367,778. Can be referred to.

As described above, the most important parameter for finally obtaining a silver halide grain having a high aspect ratio is pAg during ripening and growth.

On the surface of the tabular grains having a high silver chloride content, the principal plane of which is the (100) plane of the present invention, it is preferable to make a silver salt, which is less soluble than silver chloride, exist. Silver salts which are more insoluble than silver chloride include silver bromide, silver iodide, silver iodobromide, silver thiocyanate, silver selenocyanate and mixed crystals thereof. Silver halide is preferred.
The amount of the silver salt, which is less soluble than silver chloride, is 20 mol% or less, preferably 10 mol% or less, based on the whole grains.
More preferably 5 mol% or less, 0.001 mol%
That is all.

As a method for allowing a silver salt, which is less soluble than silver chloride, to be present on the surface of the tabular grains, a method of adding a halide salt aqueous solution and a silver salt aqueous solution having a corresponding composition by a double jet method, a fine grain emulsion addition method, and A method of using a sustained release agent of bromide ion or iodine ion can be mentioned.

In the method in which the water-soluble halide salt and the water-soluble silver salt are added by a double jet, the halogen ion is added in a free state even if the halide salt aqueous solution is diluted and added. There is a limit in trying to reduce the locality between particles. This is especially difficult for tabular grains. On the other hand, the method of adding a fine grain emulsion or the method of using a sustained-release agent is a preferable method for forming a salt, which is less soluble than silver chloride, uniformly on the surface of the grains.

The average spherical phase equivalent diameter of the fine particles in the fine grain emulsion addition method is preferably 0.1 μm or less, more preferably 0.06 μm or less. The fine particles are continuously prepared by supplying an aqueous solution of a silver salt and an aqueous solution of a salt capable of forming a silver salt having a lower solubility than silver chloride in a mixer provided in the vicinity of the reaction vessel, and immediately adding it to the reaction vessel. It can also be added after being prepared in a batch manner in another container in advance. The method using a sustained-release agent is described in JP-B-1-28594.
2. Japanese Patent Application No. 5-58039 and the like.

Gelatin is advantageously used as a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sodium alginate and starch derivatives. Sugar derivative; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone,
A wide variety of synthetic hydrophilic polymeric substances such as single or copolymers such as polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Ph
oto. Japan. No. 16. P30 (1966)
You may use the enzyme-treated gelatin as described in,
Further, a hydrolyzate or an enzymatic hydrolyzate of gelatin can also be used.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature for washing with water can be selected according to the purpose, but it is preferably selected within the range of 5 ° C to 50 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. Noodle washing method, dialysis method using semi-permeable membrane,
It can be selected from centrifugation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable depending on the purpose. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. For example, Mg, Ca, Sr, B
a, Al, Sc, Y, La, Cr, Mn, Fe, Co,
Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, O
s, Ir, Pt, Au, Cd, Hg, Tl, In, S
Metals such as n, Pb and Bi can be used. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides or hexacoordinated complex salts and tetracoordinated complex salts which can be dissolved at the time of grain formation. For example, CdBr ₂ , CdCl ₂ , Cd
(NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , Pb (CH ₃ CO
O) ₂ , K ₃ [Fe (CN) ₆ ], (NH ₄ ) ₄ [Fe
(CN) ₆ ], K ₃ IrCl ₆ , (NH ₄ ) ₃ RhCl
₆ , a metal compound such as K ₄ Ru (CN) ₆ . As a ligand of a coordination compound, halo, aco, cyano,
It can be selected from cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. Although these may use only one type of metal compound, 2
They may be used alone or in combination of three or more.

The metal compound is preferably added after being dissolved in water or a suitable organic solvent such as methanol or acetone. In order to stabilize the solution, a method of adding a hydrogen halide aqueous solution (eg, HCl, HBr) or an alkali halide (eg, KCl, NaCl, KBr, NaBr) can be used. If necessary, an acid or alkali may be added. The metal compound may be added to the reaction vessel before the formation of the particles or may be added during the formation of the particles. Further, a water-soluble silver salt (for example, AgNO ₃ ) or an aqueous alkali halide solution (for example, NaCl,
KBr, KI) and continuously added during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

The method of adding a chalcogenide compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful. In addition to S, Se, Te, cyanide, thiocyanate, selenocyanic acid, carbonate,
Phosphates and acetates may be present.

The base grain of the present invention is subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization, noble metal sensitization and reduction sensitization at any step of the silver halide emulsion production process. You can rub. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which chemically sensitized nuclei are embedded inside a grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, and a type in which a chemically sensitized nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemically sensitized nucleus can be selected according to the purpose, but it is generally preferable that at least one type of chemically sensitized nucleus is formed near the surface.

One of the chemical sensitizations that can be preferably carried out in the present invention is chalcogenide sensitization and noble metal sensitization, either alone or in combination, by TH James, The Photographic Process, No. 4. Edition, published by Macmillan, 1977, (TH James, The Th
eory of the PhotographicP
process, 4th ed, Macmillan, 1
977) pages 67-76, and can be performed using active gelatin, and can also be performed by Research Disclosure 120, April 1974, 12008; Research Disclosure 34, June 1975.
Mon, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,773,031,
No. 3,857,711, No. 3,901,714
No. 4,226,018, and No. 3,90.
4,415, and sulfur, selenium, tellurium, gold at pAg 5-10, pH 5-8 and temperature 30-80 ° C as described in GB 1,315,755.
It can be platinum, palladium or a combination of several of these sensitizers. In noble metal sensitization, for example,
Noble metal salts of gold, platinum and palladium can be used,
Of these, gold sensitization, palladium sensitization, and a combination of both are particularly preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide can be used. The palladium compound means a divalent palladium salt or a tetravalent salt. A preferred palladium compound is P
It is represented by ₂ PdX ₆ or R ₂ PdX ₄ . Where R
Represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, for example, K ₂ PdCl ₄ ,
(NH ₄ ) ₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH
₄ ) ₂ PdCl ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl
₆ or K ₂ PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
711, 4,226,018 and 4,0.
The sulfur-containing compounds described in No. 54,457 can be used. It is also possible to carry out chemical sensitization in the presence of a so-called chemical sensitizer. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526 and the above-mentioned Daffin. "Photographic Emulsion Chemistry", pages 138-143.

The emulsion of the present invention is preferably combined with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ^-4 to 1 × 10 ^-7 mol, more preferably 1 × 10 ^{-5 to} 5 × 10 ^-7 mol, per mol of silver halide. The preferable range of the palladium compound is 1 × 10 ⁻³ to 5 × 10 ⁻⁷ . The preferred range of the thiocyan compound or selenocyan compound is from 5 × 10 ⁻² to 1 × 10 ⁻⁶ .

The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1 × per mol of silver halide.
10 ^-4 to 1 × 10 ^-7 mol, more preferably 1
It is from × 10 ^{-5 to} 5 × 10 ^-7 mol.

Selenium sensitization is a preferable sensitizing method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, for example, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.),
Selenium compounds such as selenoketones and selenoamides can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization.

During grain formation of the silver halide emulsion of the present invention,
It is preferable to perform reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization.

Here, the reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, pAg1 called silver ripening.
7, a method of growing or ripening in a low pAg atmosphere, or a method of growing or ripening in a high pH atmosphere of pH 8-11 called high pH ripening. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method since the level of reduction sensitization can be finely adjusted.

Known examples of reduction sensitizers include stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide as reduction sensitizer,
Dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but the range of 10 ^-7 to 10 ^-3 mol is suitable per mol of silver halide.

The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters and amides and added during grain growth. Although it may be added to the reaction vessel in advance, it is preferable to add it at an appropriate time during grain growth. Alternatively, a reduction sensitizer may be added in advance to the water solubility of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains grow, or to add the solution continuously for a long time.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver is
A compound that acts on metallic silver to convert it into silver ions. In particular, a compound capable of converting extremely fine silver grains, which are a by-product in the process of forming silver halide grains and the process of chemical sensitization, into silver ions is effective. The silver ions generated here are, for example, silver halide, silver sulfide,
May form a sparingly soluble silver salt such as silver selenide,
Further, a silver salt which is easily soluble in water such as silver nitrate may be formed.
The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidant include ozone, hydrogen peroxide and its adducts (for example, NaBO ₂ .H ₂
O ₂ · 3H ₂ O, 2NaCO ₃ · 3H ₂ O ₂ , Na ₄ P
₂ O ₇・ 2H ₂ O ₂ , 2Na ₂ SO ₄・ H ₂ O ₂・ 2H
₂ OH), peroxy acid salts (eg K ₂ S ₂ O ₈ , K
_{2 C 2 O 6, K 2} P 2 O 8), peroxy complex compounds (e.g., K _{2 [Ti (O 2) C 2 O} 4 ] · 3H ₂ O,
4K ₂ SO ₄ .Ti (O ₂ ) OH.SO ₄ .2H ₂ O,
Na _{3 [VO (O 2) (C 2} H 4) 2 · 6H 2 O ], permanganate (e.g., KMnO _4), oxygen acid salts, such as chromates (e.g., K ₂ Cr ₂ O ₇₎ There are halogen elements such as iodine and bromine, perhalogenates (eg potassium periodate), salts of high-valent metal (eg potassium hexacyanoferrate) and thiosulfonates.

As the organic oxidant, for example, p
-Quinones such as quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B).

Preferred oxidants of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidants and quinones organic oxidants.
It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a method reverse thereto, or a method of coexisting the two simultaneously. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, for example triazaindenes, tetra Azaindenes (especially 4-hydroxy substituted (1,
Many compounds known as antifoggants or stabilizers such as 3,3a, 7) chitraazaindenes), pentaazaindenes can be added. For example, U.S. Patent Nos. 3,954,474 and 3,982,94
No. 7, JP-B-52-28660 can be used. JP-A-63-63 is one of the preferred compounds.
There are compounds described in U.S. Pat. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, it controls the crystal wall of the grains, reduces the grain size, reduces the solubility of the grains, controls the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

As the spectral sensitizing dye to be adsorbed on the base grains of the present invention, there is a methine dye, and therefore the photographic emulsion finally obtained is spectrally sensitized with methine dyes and the like. It is preferable to exhibit. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used as basic heterocyclic nuclei in cyanine dyes can be applied to these dyes. That is, for example, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus,
Imidazole nuclei, tetrazole nuclei, pyridine nuclei; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, that is, for example, indolenine nuclei, benzindolenine Nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus,
The benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus and quinoline nucleus can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, for example, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2
5-6 membered heterocyclic nuclei can be applied, such as -thioxazolidine-2,4-dione nuclei, thiazolidine-2,4-dione nuclei, rhodanin nuclei and thiobarbituric acid nuclei.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,5
No. 22,052, No. 3,527,641, No. 3,
No. 617,293, No. 3,628,964, No. 3,666,480, No. 3,672,898, No. 3,679,428, No. 3,703,377,
No. 3,769,301, No. 3,814,609
No. 3,837,862, No. 4,026,70
7, UK Patent Nos. 1,344,281 and 1,50
No. 7,803, Japanese Patent Publication No. 43-4936, No. 53-12
No. 375, JP-A Nos. 52-110618 and 52-10.
No. 9925.

In addition to the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

The preferred time of addition of the spectral sensitizing dye of the present invention is after the formation of the base grains and before the addition of the fine grains. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but U.S. Pat. Nos. 3,628,969 and 4,
It is also possible to add spectral sensitization at the same time as the chemical sensitizer as described in JP-A No. 225,666 and to perform chemical sensitization at the same time as described in JP-A-58-113928. It can be carried out prior to the sensitization, or it can be added before the completion of silver halide grain precipitation to start the spectral sensitization. Furthermore, US Pat. No. 4,255,666
It is also possible to add these said compounds separately, as taught in U.S. Pat. No. 6,096,087, i.e. to add some of these compounds prior to chemical sensitization and the rest after chemical sensitization. And at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The addition amount is 4 × per mol of silver halide.
It can be used in an amount of 10 ⁻⁶ to 8 × 10 ⁻³ mol, but in the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective. Is.

When the emulsion obtained in the present invention is used as a light-sensitive material, various additives described above are used, but various additives other than the above can be used according to the purpose.

More specifically, these additives are described in Research Disclosure Item 17643 (December 1978) and Item 18716 (December 1979).
Mon) and Item 308119 (December 1989)
Month), and the relevant parts are summarized below.

Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 page right column page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868, supersensitizer, page 649, right column 4. Whitening agent, page 24, page 647, right column, page 868, 5 Light absorber, pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dye, ultraviolet absorber 6. Binder, page 26, page 651, left column 873 to 874, page 7. Plasticizer, page 27, page 650, right Column 876 Lubricants 8. Coating aids, 26 to 27 pages 650 Right column 875 to 876 Surfactants 9. Static 27 pages 650 650 Right columns 876 to 877 Inhibitors 10. Matting agents 878 to 879 pages

Next, the compound represented by formula (I) will be described in detail below. The aliphatic hydrocarbon group represented by R ₁ and R ₂ is a linear, branched or cyclic alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 carbon atom).
To 7, particularly preferably an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-heptyl, n-hexyl, Examples include cyclohexyl. ), An alkenyl group (preferably having 2 carbon atoms)
To 12, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms, and examples thereof include vinyl and allyl. ), An alkynyl group (preferably an alkynyl group having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms, for example, propargyl and the like).

The aliphatic hydrocarbon group represented by R ₁ and R ₂ may have a substituent, and examples of the substituent include an aryl group (preferably having 6 to 12 carbon atoms, more preferably carbon atoms). An aryl group having 6 to 10, particularly preferably 6 to 8 carbon atoms, such as phenyl and p-methylphenyl, and an amino group (preferably having 0 carbon atoms).
To 20, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, and diethylamino. ), An alkoxy group (preferably having 1 to 8 carbon atoms,
More preferably 1 to 6 carbon atoms, particularly preferably 1 carbon atom
To 4 alkoxy groups, and examples thereof include methoxy and ethoxy. ), An aryloxy group (preferably an aryloxy group having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably 6 to 8 carbon atoms, and examples thereof include phenyloxy). (Preferably having 2 to 12 carbon atoms, and more preferably having 2 carbon atoms.
-10, particularly preferably an acyl group having 2 to 8 carbon atoms, and examples thereof include acetyl. ), An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and particularly preferably 2 to 8 carbon atoms, and examples thereof include methoxycarbonyl). Carbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 carbon atoms)
To 15, particularly preferably an aryloxycarbonyl group having 7 to 10 carbon atoms, and examples thereof include phenyloxycarbonyl. ), An acyloxy group (preferably an alkyloxy group having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and particularly preferably an acyloxy group having 2 to 8 carbon atoms, and examples thereof include acetoxy). 2 to 10 carbon atoms, more preferably 2 to carbon atoms
6, particularly preferably an acylamino group having 2 to 4 carbon atoms, and examples thereof include acetylamino. ), An alkoxycarbonylamino group (preferably having 2 to 1 carbon atoms)
2, more preferably, an alkoxycarbonylamino group having 2 to 10 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include methoxycarbonylamino. ),
Aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms, and particularly preferably 7 to 10 carbon atoms, and examples thereof include phenyloxycarbonylamino. ), A sulfonylamino group (preferably a C1-C10, more preferably a C1-C6, particularly preferably a C1-C4 sulfonylamino group such as methanesulfonylamino), and a sulfamoyl group. (Preferably a sulfamoyl group having 0 to 10 carbon atoms, more preferably 0 to 6 carbon atoms, and particularly preferably 0 to 4 carbon atoms, and examples thereof include sulfamoyl and methylsulfamoyl.), A carbamoyl group (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably carbon. From 1 to 4 carbamoyl groups, for example carbamoyl,. Etc. methylcarbamoyl and the like), an alkylthio group (preferably having from 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to carbon atoms
And 4, for example, methylthio, ethylthio, carboxymethylthio and the like. ), An arylthio group (preferably having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably an arylthio group having 6 to 8 carbon atoms, such as phenylthio, etc.), a sulfonyl group (preferably carbon). C1-8, more preferably C1-6, especially preferably C1-4
Is a sulfonyl group, and examples thereof include methanesulfonyl. ), A sulfinyl group (preferably having 1 carbon atom)
To 8, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms, and examples thereof include methanesulfinyl group. ), A ureido group (preferably a ureido group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms, and examples thereof include ureido and methylureido). , Mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, heterocyclic group (eg imidazolyl, pyridyl) and the like. . These substituents may be further substituted. When there are two or more substituents, they may be the same or different. The substituent is preferably an amino group, an alkoxy group, a carboxyl group, a hydroxy group, a halogen atom, a cyano group, a nitro group, more preferably an alkoxy group, a carboxyl group, a hydroxy group, a halogen atom, and further preferably , An amino group, a carboxyl group and a hydroxy group, and particularly preferably a hydroxy group and a carboxyl group.

The aliphatic hydrocarbon group represented by R ₁ and R ₂ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 7 carbon atoms,
More preferably, it is an alkyl group having 1 to 4 carbon atoms. Specifically, methyl, ethyl, n-propyl, iso-propyl, n-butyl, benzyl, hydroxymethyl, carboxymethyl and 5-imidazolylmethyl are preferable, and particularly methyl, ethyl, n-propyl, iso-propyl,
N-butyl is preferred. The aryl group represented by R ₁ and R ₂ may be a single ring or may form a condensed ring with another ring, and preferably has 6 to 20 carbon atoms, and more preferably has 6 to 16 carbon atoms. , And more preferably an aryl group having 6 to 12 carbon atoms.

The aryl group represented by R ₁ and R ₂ is preferably monocyclic or bicyclic, and examples thereof include phenyl and naphthyl, more preferably phenyl. The aryl group represented by R ₁ and R ₂ may have a substituent, and examples of the substituent include alkyl groups in addition to those listed as the substituents of the aliphatic hydrocarbon represented by R ₁ and R _2. , Alkenyl groups, alkynyl groups and the like.

The heterocyclic group represented by R ₁ and R ₂ is
3 to 1 containing at least one of N, O or S atoms
It is a 0-membered saturated or unsaturated hetero ring, which may be a single ring or may form a condensed ring with another ring.

The heterocycle is preferably a 5- to 6-membered aromatic heterocycle, more preferably a 5- to 6-membered aromatic heterocycle containing a nitrogen atom, and further preferably a 1- to 2-atom nitrogen atom. It is a 5- to 6-membered aromatic heterocycle including.

Specific examples of the heterocycle include, for example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole,
Pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline,
Examples thereof include pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole and oxazole. Preferably as a heterocycle, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, thiadiazole, oxadiazole, quinoline,
Phthalazine, quinoxaline, quinazoline, cinnoline,
Tetrazole, thiazole, oxazole, more preferably imidazole, pyrazole, pyridine, pyrazine, indole, indazole, thiadiazole,
Oxadiazole, quinoline, thiazole, oxazole, more preferably imidazole, pyridine,
Quinoline is preferable, and imidazole and pyridine are particularly preferable.

The heterocyclic group represented by R ₁ and R ₂ may have a substituent, and examples of the substituent include those enumerated as the substituents of the aliphatic hydrocarbon represented by R ₁ and R _2. other,
Examples thereof include an alkyl group, an alkenyl group and an alkynyl group.

R ₁ is preferably an alkyl group having 1 to 7 carbon atoms or a phenyl group, and more preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group. R ₂ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom.

The alkylene group represented by L _{1 to} L ₅ may be linear, branched or cyclic, and is preferably a linear or branched alkylene group. The number of carbon atoms forming the alkylene group is preferably 1 to 10, more preferably 1 to 6
And particularly preferably 1 to 4.

L ₁ and L ₅ are preferably methylene, and more preferably unsubstituted methylene. L ₂ , L
₃ , and L ₄ are preferably methylene and ethylene, and more preferably methylene. Also, L _{1 to} L ₅
The alkylene group represented by may have a substituent, and examples of the substituent include an alkenyl group, an alkynyl group, etc., in addition to those listed as the substituents of the aliphatic hydrocarbon represented by R ₁ and R _2. Can be mentioned.

M and n represent 0 or 1, and preferably (m, n) = (1,0), (m, n) = (0,
1), (m, n) = (0,0), and more preferably (m, n) = (1,0), (m, n) = (0,0),
And particularly preferably (m, n) = (0,0).

The alkylene group represented by W ¹ and W ² may be linear, branched or cyclic, and is preferably a linear or branched alkylene group. The alkylene group has preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 4 carbon atoms. Examples of the alkylene group represented by W ¹ and W ² include ethylene, propylene, trimethylene, 1,2-cyclohexylene and the like, preferably ethylene, propylene, trimethylene and tetramethylene, more preferably ethylene,
It is trimethylene. The arylene group represented by W ¹ or W ² may be a single ring or may form a condensed ring with another ring, and preferably has 6 to 20 carbon atoms, and more preferably has 6 to 16 carbon atoms. , And more preferably an arylene group having 6 to 12 carbon atoms.

The arylene group represented by W ¹ and W ² is preferably monocyclic or bicyclic, and examples thereof include phenylene and naphthylene, and more preferably phenylene. The aralkylene group represented by W ¹ or W ² preferably has 7 to 21 carbon atoms, more preferably 7 to 1 carbon atoms.
7, more preferably an aralkylene group having 7 to 13 carbon atoms, and examples thereof include o-xylenyl. W ¹ ,
The divalent nitrogen-containing heterocyclic group represented by W ² is preferably a 5- or 6-membered heteroatom having nitrogen, and examples thereof include imidazolyl. Also, W ¹ , W ²
May have a substituent, and as the substituent, R ₁ , R ₂
In addition to the examples of the substituent of the aliphatic hydrocarbon represented by, alkenyl group, alkynyl group and the like can be mentioned.

D is a single bond, --O--, --S--, --N (R
w) -represents. The aliphatic hydrocarbon group and aryl group represented by Rw have the same meaning as the aliphatic hydrocarbon group and aryl group represented by R ₁ and R ₂ . The aliphatic hydrocarbon group and aryl group represented by Rw may have a substituent,
Examples of the substituent include the alkenyl group and the alkynyl group, in addition to those listed as the substituents of the aliphatic hydrocarbon represented by R ₁ and R ₂ .

The substituent of Rw is preferably a carboxyl group, a phosphono group, a hydroxy group or a sulfo group,
More preferably, it is a carboxyl group. Rw is preferably an optionally substituted alkyl group having 1 to 8 carbon atoms (eg methyl, carboxymethyl) or an aryl group having 6 to 10 carbon atoms (eg phenyl).

V represents an integer of 0 to 3, and v is 2 or 3.
Then W ¹ -D may be the same or different. v is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0. w represents an integer of 1 to 3, and when w is 2 or 3, W ₂ may be the same or different.
w is preferably 1 or 2. (W ¹ -D) v -
Examples of (W ² ) w − include the following.

[0093]

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[0094]

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More preferably (W ¹ -D) v-(W ² ) w-, ethylene, propylene, trimethylene,
It is 2,2-dimethyltrimethylene, and ethylene and trimethylene are particularly preferable.

The cation represented by M ₁ , M ₂ , M ₃ and M ₄ may be an organic cation or an inorganic cation. When there are two or more cations in the same molecule, they may be different cations. Examples of the cation include alkali metals (eg, Li ⁺ , N
a ⁺ , K ⁺ , Cs ^+, etc.), alkaline earth metals (eg, Ca ²⁺ , Mg ^2+, etc.), ammonium (eg, ammonium, tetraethylammonium, etc.), pyridinium, phosphonium (eg, tetrabutylphosphonium,
Tetraphenylphosphonium).
Preferably, it is an inorganic cation, and more preferably, it is an alkali metal ion. Among the compounds represented by the general formula (I), preferably the following general formula (II) or (III)
It is a compound represented by these. General formula (II)

[0097]

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(In the formula, R ₁ 'represents an aliphatic hydrocarbon group.
The aliphatic hydrocarbon group represented by R ₁ 'has the same meaning as the aliphatic hydrocarbon group represented by R ₁ in formula (I), and the preferred range is also the same. L ₁ , L ₃ , L ₄ , L ₅ ,
m, n, W ¹ , W ² , D, v, w, M ₁ , M ₂ , M ₃ and M ₄ have the same meanings as those in formula (I), and the preferred ranges are also the same. ) General formula (III)

[0099]

[Chemical 6]

(In the formula, R ₁ ″ represents an aryl group.
The aryl group represented by R ₁ ″ has the same meaning as the aryl group represented by R ₁ in formula (I), and the preferred range is also the same. L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , m,
Each of n, W ¹ , W ² , D, v, w, M ₁ , M ₂ , M ₃ and M ₄ has the same meaning as in formula (I), and the preferred range is also the same. )

Of the compounds represented by the general formula (II), the compounds represented by the following general formula (IV) are more preferred. General formula (IV)

[0102]

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[0103] (In the formula, R ₁ 'is R ₁ in the general formula (II)'
It is synonymous with and the preferable range is also the same. L ₃ , L
₄ , m, W ¹ , W ² , D, v, w, M ₁ , M ₂ , M ₃ and M ₄ have the same meanings as those in formula (I), and the preferred ranges are also the same. )

Of the compounds represented by the general formula (III), the compound represented by the following general formula (V) is more preferable. General formula (V)

[0105]

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(In the formula, R ₁ ″ represents R in the general formula (III).
It has the same meaning as ₁ ″ and the preferred range is also the same. L ₂ ,
L ₃ , L ₄ , m, W ¹ , W ² , D, v, w, M ₁ , M
₂ , M ₃ and M ₄ have the same meanings as those in formula (I), and the preferred ranges are also the same. )

Among the compounds represented by the general formula (IV), the compound represented by the following general formula (VI) is more preferable. General formula (VI)

[0108]

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[0109] (In the formula, R ₁ 'is R ₁ in the general formula (II)'
It is synonymous with and the preferable range is also the same. W ²¹ is an alkylene group having 2 to 8 carbon atoms for W ² in the general formula (I), and the preferred range is also the same. L ₃ , L ₄ , M
₁ , M ₂ , M ₃ and M ₄ have the same meanings as those in formula (I), respectively, and the preferred ranges are also the same. Of the compounds represented by the general formula (V), more preferred are the compounds represented by the following general formula (VII). General formula (VII)

[0110]

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(In the formula, R ₁ ″ represents R in the general formula (III).
It has the same meaning as ₁ ″ and the preferred range is also the same. W ²¹ is an alkylene group having 2 to 8 carbon atoms for W ² in the general formula (I), and the preferred range is also the same. L ₂ , L ₃ ,
L ₄ , M ₁ , M ₂ , M ₃ and M ₄ have the same meanings as those in formula (I), and the preferred ranges are also the same. )

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

[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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The above compounds may be used in the form of salts. The compound represented by the general formula (I) of the present invention is, for example, Inorganic Chemistry Vol. 8 (No. 6) 1374.
Page (1969) (Inorganic Chemis
try, 8 (6), 1374 (1969). ) It can be synthesized according to the described method.

The central metal used in the metal chelate compound of the present invention is, for example, Fe (III), Mn (III), Co (II
I), Rh (II), Rh (III), Au (III), Au (II), Ce (I
V). Fe (III) is preferred. The metal chelate compound of the present invention can be synthesized by reacting the compound represented by the general formula (I) with a metal salt. Examples of the metal salt reacted with the compound represented by the general formula (I) include ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, and the like. Examples include ferric oxide.

In the present invention, the metal chelate compound in the processing solution having a bleaching ability may be used alone or in combination of two or more kinds, but 20 mol% or more of the compound forming the metal chelate compound is used. Preferably occupied by the compound represented by the above general formula (I), more preferably 25
˜100 mol%, most preferably 35-100%.

The metal chelate compound of the present invention may be isolated as a metal chelate compound, or may be a compound represented by the general formula (I) and a metal salt such as ferric sulfate or ferric chloride. An iron salt, a ferric nitrate salt, a ferric phosphate salt, etc. may be used by reacting in a solution. The compound represented by the general formula (I) is used in a molar ratio of 1.0 or more to the metal ion. This ratio is preferably large when the stability of the metal chelate compound is low, and is usually in the range of 1 to 30.

The metal chelate compound of the present invention is added to the processing solution having a bleaching ability in an amount of 0.
The range of 003 to 1.00 mol / liter is suitable,
The range of 0.01 to 0.50 mol / liter is preferable,
More preferably, it is in the range of 0.05 to 0.40 mol / liter. Further, a small amount may be contained in a fixing solution or an intermediate bath between the color development and the desilvering step. As the bleaching agent, the metal chelate compound of the present invention is used, but known bleaching agents may be used in combination to the extent that the effects of the present invention are not impaired (preferably 2/3 or less in molar ratio).

In the present invention, from the viewpoint of having sufficient solubility even under severe low temperature conditions, ferric ethylenediaminetetraacetic acid complex salt and / or ethylenediamine-N-2-carboxyphenyl described in JP-A-5-66527. −
It is preferable to use N, N ′, N′-ferric triacetate complex salt in combination.

Other bleaching agents that can be used in combination include, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, and nitro compounds. Typical bleaching agents are organic complex salts of iron (III) such as diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, glycol etherdiaminetetraacetic acid, JP-A-4-
No. 121739, bleaching agents such as 1,3-propylenediaminetetraacetic acid iron complex salts in the lower right column of the fourth page to the upper left column of the fifth page, and carbamoyl bleaching described in JP-A-4-73647. Agents, bleaching agents having a heterocycle described in JP-A-4-174432, bleaching agents described in EP-A-520457, including N- (2-carboxyphenyl) iminodiacetic acid ferric complex salts, Patent Publication No. 5
Bleach described in 01479, EP 5671
26, a bleaching agent described in JP-A-4-127145, and (11) in JP-A-3-144446.
Examples thereof include ferric aminopolycarboxylic acid salts or salts thereof described on the page, but are not limited thereto.

Examples of the bleaching agent contained in the processing solution having a bleaching ability include other inorganic oxidizing agents such as red blood salt, ferric chloride, dichromate, persulfate, bromate and hydrogen peroxide. , Organic acid iron (III) complex salts are known.

The organic acid iron (III) complex salt contained in the bleaching treatment solution of the present invention may be used as an alkali metal salt or an ammonium salt. Examples of the alkali metal salt include lithium salt, sodium salt and potassium salt, and examples of the ammonium salt include ammonium salt and tetraethylammonium salt.

In the present invention, as a bleaching agent for a processing solution having a bleaching ability, in addition to the above-mentioned bleaching agent comprising an iron (III) complex salt of an organic acid, the above-mentioned inorganic oxidizing agent may be used in combination as a bleaching agent. When an inorganic oxidizing agent is used in combination, the total concentration of iron (III) complex salt is preferably 0.005 to 0.050 mol / liter.

The magnetic recording layer and support preferably used in the present invention will be described. By using such a magnetic recording layer and a support, a surprising effect was found that problems such as clogging of a circulatory system filter were improved. In particular, the frequency of clogging of the circulation filter in the washing bath or stabilizing bath, which is a post-process of the bleach-fixing bath, was significantly reduced.

When the light-sensitive material of the present invention is used as a color negative film, the support may be any one of the international publication WO90 /
No. 04205, FIG. Those having the magnetic recording layer described in 1A are preferable. Such a magnetic recording layer is formed by coating a support with an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder. Magnetic particles used in the present invention include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co coated magnetite ,, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic Alloy, Hexagonal Ba ferrite, Sr ferrite, Pb
Ferrite, Ca ferrite, etc. can be used. Co deposition γ
Co-deposited ferromagnetic iron oxide such as Fe ₂ O ₃ is preferred. The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like. The specific surface area of S _BET is preferably 20 m ² / g or more, 30
Particularly preferred is m ² / g or more. Saturation magnetization (σs) of ferromagnet
Is preferably 3.0 × 10 ⁴ to 3.0 × 10 ⁵ A / m, particularly preferably 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161032.
In addition, the surface of the inorganic particles described in JP-A-4-259911 and 5-81652 is
Magnetic particles coated with an organic substance can also be used.

The binder used for the magnetic particles is a thermoplastic resin, a thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer described in JP-A-4-219569, a natural product weight. Coalescence (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The above resin has a Tg of -40 ° C to 300 ° C and a weight average molecular weight of 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based crosslinking agent include isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates with polyalcohol (for example, 3mol of isocyanate and 1m of trimethylolpropane
ol reaction product), and polyisocyanates formed by condensation of these isocyanates.
For example, it is described in JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill or the like is preferable as in the method described in JP-A-6-35092, and the combined use is also preferable. Dispersants described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm.
m, more preferably 0.3 μm to 3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100.
And more preferably from 1: 100 to 30: 100. The coating amount of the magnetic particles 0.005~ 3g / m ^2, preferably from 0.01 to 2
g / m ² , more preferably 0.02 to 0.5 g / m ² . The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50,
03 to 0.20 is more preferable, and 0.04 to 0.15 is particularly preferable.
The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. As a method of applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze, an impregnation, a reverse roll,
Transfer rolls, gravure, kisses, casts, sprays, dips, bars, extrusions and the like can be used, and the coating solutions described in JP-A-5-341436 are preferred.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, anti-adhesion and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. For photosensitive materials having a magnetic recording layer, see US Pat.
5,229,259, 5,215,874 and EP 466,130.

The material for the support is, for example, JP-A-4-124.
Various plastic films described in No. 636, page 5, upper right column, line 1 to page 6, upper right column, line 5 can be used, and preferred are cellulose derivatives (for example, diacetyl-,
Triacetyl-, propionyl-, butanoyl-, acetylpropionyl-acetate) and JP-B-48-404
The polyester described in No. 14 (for example, polyethylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene naphthalate) can be mentioned. The support of the film used in the case of using the light-sensitive material of the present invention as a color negative film has a higher draining effect and can reduce the mixing of the pre-bath component to the next step, and therefore polyethylene terephthalate, Polyethylene naphthalate described in Functional Materials, February 1991, pages 20 to 28 is preferable.

Next, the polyester support preferably used in the present invention will be described. For details, including a photosensitive material, a treatment, a cartridge and examples described later, open technical report, official technique number 94-6023 (Invention Society; 1994.3.15.). The polyester used in the present invention is formed by using diol and aromatic dicarboxylic acid as essential components. As aromatic dicarboxylic acids, 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic acid Examples of the acid, isophthalic acid, phthalic acid, and diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Particularly preferred among them is polyethylene 2,
It is 6-naphthalate. Average molecular weight range is about 5,000
Or 200,000. The polyester of the present invention has a Tg of 50.
C. or higher, more preferably 90.degree. C. or higher.

Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or higher and lower than Tg, and more preferably Tg−20 ° C. or higher and lower than Tg in order to prevent the curling tendency. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is 0.1 to 1500 hours, more preferably 0.5 to 200 hours. The heat treatment of the support may be performed in the form of a roll, or may be performed while transporting the support in the form of a web.
Surface irregularities may be imparted (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ may be applied) to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and raising the ends only slightly to prevent cut-out of the core. These heat treatments are performed after forming the support, after surface treatment,
It may be carried out at any stage after application of the back layer (antistatic agent, slip agent, etc.) and after application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. Also, to prevent light piping,
The purpose can be achieved by kneading dyes or pigments commercially available for polyesters such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to carry out a surface treatment in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable. Next, the undercoating method will be described. It may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid,
Examples include a copolymer using a monomer selected from acrylic acid, itaconic acid, maleic anhydride and the like as a starting material, polyethylene imine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcin and p-chlorophenol. As a gelatin hardening agent for the undercoat layer, chromium salts (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-) are used.
Hydroxy-S-triazine, etc.), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids and carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Z
_{nO, TiO 2, SnO 2,} Al 2 O 3, In 2 O 3, SiO 2, MgO, BaO,
MoO ₃ , at least one selected from V ₂ O ₅ has a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. Fine particles of oxides or composite oxides thereof (Sb, P, B, In, S, Si, C, etc.), and sol-like metal oxides or fine particles of these composite oxides. The content in the photosensitive material should be between 5 and
500 mg / m ² are preferred and particularly preferably 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably from 1/300 to 100/1, more preferably from 1/100 to 100/5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.
It is 25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball with a diameter of 5 mm is transported at 60 cm / min (25
℃, 60% RH). In this evaluation, even if the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level. Examples of the slip agent usable in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes such as polydimethyl siloxane, polydiethyl siloxane, poly Styrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethylmethacrylate, poly (methylmethacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow, and the average particle size is 0.9 to 1.
It is preferable that 90% or more of the total number of particles be contained in one time. It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate /
Methacrylic acid = 9/1 (molar ratio, 0.3 µm)), polystyrene particles (0.25 µm), colloidal silica (0.03 µm).

The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Wherein the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to any of red light and a multilayer silver halide color photographic light-sensitive material. In general, the arrangement of the unit light-sensitive layers is, in order from the support side, a red light-sensitive layer, The color-sensitive layer and the blue-sensitive layer are provided in this order. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
Couplers, DIR compounds and the like described in JP-A Nos. 61-20037 and 61-20038 may be contained, and a color mixture inhibitor may be contained as usually used.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also,
JP-A-57-112751, 62-200350
As described in JP-A Nos. 62-206541 and 62-206543, a low-speed emulsion layer may be provided on the side farther from the support and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low-sensitivity blue-sensitive layer (BL) / High-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
And so on.

Further, as described in JP-B-55-34932, layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. JP-A-56-25738 and JP-A-62-6393.
As described in the specification of JP-A No. 6, the blue light-sensitive layer / GL / RL / GH / RH may be arranged in this order from the farthest side from the support.

Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.

Also, in the case of four or more layers, the arrangement may be changed as described above.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.

In the photographic light-sensitive material of the present invention, at least one silver halide emulsion layer provided on a support has a silver halide emulsion of the present invention of 30% or more, preferably 50% or more, and more preferably. It is a silver halide photographic light-sensitive material containing 70% or more.

About 3 silver halides other than the silver halide of the present invention contained in the photographic emulsion layer of the photographic light-sensitive material of the present invention are contained.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide containing 0 mol% or less of silver iodide is preferable. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. However, it is preferable that the content of silver bromide contained in the entire light-sensitive material is low, and the content of silver iodide is also low.

The silver halide grains other than the silver halide of the present invention in the photographic emulsion include those having regular crystals such as cubic, octahedral and tetradecahedral, and irregular such as spherical and tabular. Those having different crystal forms, those having crystal defects such as twin planes, or a composite form thereof may be used.

The grain size of silver halides other than the silver halide of the present invention may be fine grains of about 0.2 micron or less, or large grains having a projected area diameter of up to about 10 microns. It may be a dispersion emulsion.

The silver halide emulsion used in the present invention is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The methods of physical ripening, chemical ripening and spectral sensitization can be carried out in the same manner as in the above high silver chloride (100) tabular grains.

The above-mentioned various additives are used in the emulsion relating to the present invention. In addition to the above, various additives are used in the same manner as the above-mentioned high silver chloride (100) tabular grains according to the purpose. it can.

The light-sensitive material of the present invention comprises a light-sensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more emulsions differing in at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
The term "silver halide particles having a fogged inside or surface thereof" means silver halide grains which can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. . A method for preparing silver halide grains having the inside or the surface of the grains fogged is described in U.S. Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner core of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is 0.01 to 0.7.
5 μm, particularly preferably 0.05 to 0.6 μm, is preferred. Also,
The grain shape is not particularly limited, and may be regular grains or polydispersed emulsions, but may be monodispersed (at least 95% of the weight or the number of silver halide grains is within ± 40% of the average grain size). Having a particle size of 1).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. .

The fine grain silver halide has a silver chloride content of 0 to 100 mol%, and if necessary, silver bromide and / or
Alternatively, it may contain silver iodide. Preferably, it contains 0.5 to 10 mol% of silver bromide.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

Fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains.

The amount of silver coated on the light-sensitive material of the present invention was 8.0 g.
/ M ² or less is preferable, 6.0 g / m ² or less is more preferable, and 4.5 g / m ² or less is most preferable.

Known photographic additives that can be used in the present invention are also described in the above-mentioned three Research Disclosures, and the related portions are shown in Table 1 below.

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,98
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in JP-A No. 7 or 4,435,503 to the photosensitive material.

The light-sensitive material of the present invention can be prepared according to US Pat.
0,454, 4,788,132, JP-A-62
It is preferable to include a mercapto compound described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Laid-Open No. 1-1060.
No. 52, it is preferable to contain a compound which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver produced by the development processing.

The light-sensitive material of the present invention has the international publication WO88 /
No. 04794, a dye dispersed by the method described in JP-A No. 1-502912 or EP 317,308A,
U.S. Pat. No. 4,420,555;
It is preferable that the dye described in No. 8 be contained.

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by formula (I) in US Pat. No. 5,066,576, column 1, lines 45 to 55; a coupler represented by formula (I) in paragraph 0008 of JP-A-4-274425; Couplers according to claim 1 of page 4 of EP 498,381A1 (especially D-35 on page 18); couplers of formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y- 54 (p. 41)); US
Couplers represented by formulas (II) to (IV) at 4,476,219, column 7, lines 36 to 58 (especially II-17,19 (column 17), II-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (page 11, lower right), L-
68 (lower right of page 12), L-77 (lower right of page 13); A-4 -6 of EP 456,257
3 (p. 134), A-4 -73, -75 (p. 139); M-4, -6 in EP 486,965
(Page 26), M-7 (page 27); EP-571,959A M-45 (page 19);
5-204106 (M-1) (page 6); JP-A-4-362631, paragraph 0237 M-
twenty two. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); C-7,10 (page 35) of JP-A-4-43345, 3
4,35 (page 37), (I-1), (I-17) (pages 42 to 43); JP-A-6-67385
A coupler represented by the general formula (Ia) or (Ib) according to claim 1. Polymer coupler: P-1, P-5 (p. 11) of JP-A-2-44345.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII), and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), (2) of US 4,837,136 (column 8),
Colorless masking couplers of formula (A) in claim 1 of WO 92/11575 (especially the exemplified compounds on pages 36 to 45) are preferred. Examples of the compound (including a coupler) which releases a photographically useful compound residue by reacting with an oxidized developing agent include the following. Development inhibitor releasing compound: EP 37
Compounds represented by the formulas (I), (II), (III) and (IV) described on page 11 of 8,236A1 (especially T-101 (page 30), T-104 (page 31), T-113 ( 36
T-131 (p. 45), T-144 (p. 51), T-158 (p. 58)), EP436, 93
Compounds of formula (I) described on page 7 of 8A2 (particularly D-4
9 (page 51)), the compound of formula (1) of EP 568,037A (especially (23) (page 11)), and the compounds of formulas (I), (II), Compounds represented by (III) (especially I-
(1)); Bleaching accelerator releasing compounds: compounds represented by formulas (I) and (I ′) on page 5 of EP 310,125A2 (especially (60) and (6) on page 61)
1)) and the compound represented by formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7)); Ligand releasing compound: US
Compound represented by LIG-X described in claim 1 of 4,555,478 (especially compound on lines 21 to 41 of column 12); Leuco dye-releasing compound: compound 1 of columns 3 to 8 of US 4,749,641
~ 6; Fluorescent dye-releasing compound: C in claim 1 of US 4,774,181
Compounds represented by OUP-DYE (particularly compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound: US
4,656,123, the compounds of formulas (1), (2) and (3) in column 3 (especially (I-22) in column 25) and EP 450,637A2
ExZK-2, p. 75, lines 36-38; Compound which releases a group which becomes a dye only when it is cleaved: Formula (I) of claim 1 of US 4,857,447
(Especially Y-1 to Y-19 in columns 25 to 36)
.

As the additives other than the coupler, the following are preferable. Dispersion medium of oil-soluble organic compound: P-3,5, JP-A-62-215272
16,19,25,30,42,49,54,55,66,81,85,86,93 (140-144
Page); Latex for impregnation of oil-soluble organic compounds: US 4,199,
Latex described in 363; Oxidized developer scavenger: a compound represented by the formula (I) in column 2, lines 54 to 62 of US Pat. ) (Column 4-
5), US Pat. No. 4,923,787, columns 5 to 10 of formula (particularly compound 1 (column 3); stain inhibitor: EP 298321A 4
Formulas (I) to (III) on page 30-33, especially I-47, 72, III-1, 27 (24
-48 pages); Anti-fading agent: A-6, 7, 20, 21, 23, 2 of EP 298321A
4,25,26,30,37,40,42,48,63,90,92,94,164 (69-118
P.), US 5,122,444, columns 25-38 II-1 to III-23, especially
III-10, EP 471347A I-1 to III-4 on pages 8 to 12, especially II-
2, US 5,139,931 columns 32-40 A-1 to 48, especially A-39,
42; Material that reduces the amount of color enhancer or color mixture inhibitor used: I-1 to II-15 on pages 5 to 24 of EP 411324A, especially I-4
6; Formalin scavenger: EP 477932A, pages 24 to 29 SCV-1 to 28, especially SCV-8; Hardener: JP-A 1-214845
Formulas in columns 13-23 of H-1,4,6,8,14, US 4,618,573 on page 17
Compounds (H-1 to 54) represented by (VII) to (XII),
214852, page 8, lower right, compound represented by formula (6) (H-1 to 7
6), especially the compound described in claim 1 of H-14, US 3,325,287; Development inhibitor precursor: P-2 of JP-A-62-168139
4,37,39 (pages 6-7); compounds as claimed in claim 1 of US 5,019,492, in particular column 7, 28,29; preservatives, fungicides: US
4,923,790 columns 3 to 15 I-1 to III-43, especially II-1,
9,10,18, III-25; Stabilizer, antifoggant: US 4,923,79
I-1 to (14) in columns 6 to 16 of 3, especially I-1,60, (2), (13), U
S 4,952,483 columns 25-32 compounds 1-65, especially 36:
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-18 of JP-A-3-156450
A-1 to b-20, especially a-1,12,18,27,35,36, b-5,27 to 29
Pages V-1 to 23, especially V-1, EP 445627A pages 33 to 55 FI-
1 to F-II-43, especially FI-11, F-II-8, EP 457153A 17 to 28
Pages III-1 to 36, especially III-1,3, WO 88/04794 8-26
Microcrystalline dispersion of Dye-1 to 124, compounds 1 to 22 of EP 319999A, pages 6 to 11, especially compound 1, compounds D-1 to 87 (3) represented by formulas (1) to (3) of EP 519306A. ~ Page 28), US 4,26
8,622 compounds represented by the formula (I) (columns 3 to 1)
0), compounds (1) to (4) of US Pat.
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
9), and the compounds (3) to (6) represented by the formula (I) in EP 520938A.
6) (Pages 10 to 44) and compound HBT-1 represented by formula (III)
~ 10 (page 14), a compound represented by formula (1) in EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Japanese Patent Publication No.
Suitable for the lens-fitted film unit described in 3-39784. Suitable supports that can be used in the present invention are
For example, the RD. Page 28 of No.17643, 6 of No.18716
From page 47, right column to page 648, left column, and No. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and 16 μm or less. Particularly preferred. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is the time until the film thickness reaches 1/2 when the saturated film thickness is 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds. It is defined as
The film thickness means the film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and T _1/2 is a photograph science and engineering of A. Green et al. (Photogr.Sci.Eng.), 19 square, 2, 124 to 129 can be measured by using a swellometer (swelling meter) of the type. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the following formula: (maximum swelling film thickness-film thickness) / film thickness.

The photographic material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
In this back layer, the above-mentioned light absorber, filter dye,
It is preferable to contain an ultraviolet absorber, an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, and a surfactant. The swelling ratio of this back layer is 150 ~ 500
% Is preferred. In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling ratio of this back layer is 150-50.
0% is preferable.

The light-sensitive material of the present invention is the same as the above-mentioned RD. No.176
No. 18716, No. 18716, left column to right column, and No. 18716
No. 307105, pages 880 to 881 can be used for development.

The wrapping material (patrone) for storing the light-sensitive material of the present invention may be any existing or known one, and in particular, one having the shape described in FIGS. 1 to 3 of US Pat. No. 4,834,306 or FIG. 1 of US Pat. No. 4,846,418
~ Those described in Fig. 3, or US Patent No. 5,296,887
The ones shown in Fig. 1 to Fig. 7 are preferable. The film format used in the present invention is the Japanese Industrial Standard "JI
SK-7519 (1982 type), including the 135 type,
123047, 4-123059, 4-123051, 4-125560
In addition to the formats described in Nos. 4-156450 and 4-287040, any known format can be used.

In the present invention, it is preferable that the processed and dried light-sensitive material be roll-shaped and housed in a cartridge. As a cartridge to be stored, US Pat.
1,840, 5,296,887, JP-A-4-121739, 4-12
3047, 4-123059, 4-125560, 4-287040,
The cartridges and / or cartridges described in Nos. 6-19051, 6-19062 and 6-35123 are preferable, but not limited thereto. Among them, US Patent 5,
The cartridge described in 296,887 is particularly preferable. The features of the cartridge preferable in the present invention will be described below, but the present invention is not limited thereto. The processed photosensitive material is preferably stored in a roll in a cartridge, and particularly preferably in a roll with the emulsion surface inside. -The shape of the cartridge to be stored is not particularly limited,
The inner wall with which the photosensitive material is in contact preferably has a columnar shape along the outer periphery of the photosensitive material roll, since it is difficult for the photosensitive material to have unnecessary folds. · The handling and storability point, bottom is 1.0～5.0Cm ² and height 1.0～5.0Cm, cylindrical or prismatic in particular at a base of 2.2～3.8Cm ² and height 3.0~4.0cm Are preferred.・ A cartridge dedicated to storage may be used, or a cartridge of the same shape as the cartridge (also called a cartridge) that stored the photosensitive material before shooting, and the processed photosensitive material itself is stored before shooting. The same photosensitive material may be stored in the same cartridge.・ You may store a roll in advance, or
It may be a storage method in which it is wound up on a spool in the cartridge. At this time, the image portion where the roll center side is first photographed may be the image portion where the roll outer periphery side is first photographed. From the viewpoint of image storability (particularly, light fading), a light-shielding cartridge is preferable, and it is preferable that the photosensitive material is not exposed from the cartridge. The bottom surface and / or the top surface may be open, and the shape may be such that a column or a prism can be divided in a vertical direction. -The outside of the cartridge may have a protrusion and / or a groove that can be jointed with a single substance and / or other components. -In the case of a cartridge having a spool, it is preferable that the spool does not protrude from the cartridge body from the viewpoint of handleability.

In the present invention, the main material of the film cartridge may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonionic, anionic, cationic and betaine surfactants or polymers can be preferably used. These antistatic patrones are described in JP-A 1-312537 and JP-A 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be the same size as the current 135 size, or the size of the current 135 size 25 mm cartridge can be reduced to 22 mm for miniaturization of the camera.
The following is also effective. The volume of the patrone case is preferably 30 cm ³ or less, more preferably 25 cm ³ or less. The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.

Further, the film cartridge used in the present invention may be a cartridge that rotates the spool to feed the film. Further, a structure may be employed in which the leading end of the film is housed in the cartridge body, and the leading end of the film is sent out from the port of the cartridge by rotating the spool shaft in the film sending direction. These are US 4,834,30
6, 5,226,613. The photographic film used in the present invention may be a so-called raw film before development, or may be a photographic film subjected to development processing. Also, the raw film and the developed photographic film may be stored in the same new cartridge or different cartridges.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, U.S. Pat.
Indoaniline compounds described in No. 42,597, No. 3,342,5
No. 99, Research Disclosure No. 14,850 and the same
The Schiff base type compounds described in Nos. 15,159, the aldol compounds described in No. 13,924, the metal salt complexes described in US Pat. No. 3,719,492, and the urethane compounds described in JP-A No. 53-135628 can be mentioned. The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical compounds are JP-A-56-64339 and JP-A-57-14454.
7 and 58-115438.

The format of the color negative film used in the present invention is the Japanese Industrial Standard "JIS.K-7519".
(1982) ”, the 135 type,
In addition to the format described in -287040, any known format can be used.

The light-sensitive material of the present invention is described in JP-B-2-32615,
It is also effective when applied to the film unit with lens described in Japanese Utility Model Publication No. 3-39784.

In the present invention, the imagewise exposed light-sensitive material is processed with a color developing solution, desilvered, and then washed with water and / or a stabilizing solution. In the desilvering process, basically, a bleaching treatment is carried out with a processing solution having a bleaching ability, and then a fixing treatment is carried out with a processing solution having a fixing ability. As described above, the bleaching process and the fixing process may be performed separately, or may be performed simultaneously with a bleach-fixing solution having both the bleaching ability and the fixing ability (bleach-fixing treatment). The bleaching treatment, the fixing treatment and the bleach-fixing treatment may each be performed in one tank or two or more tanks.

The processing solution having a bleaching ability in the present invention means a processing solution containing a bleaching agent among processing solutions used in the desilvering process, and specifically, a bleaching solution and a bleach-fixing solution. Say. In the present invention, the processing solution having a bleaching ability is preferably a bleach-fixing solution from the viewpoint of exerting its effect remarkably. Further, the processing solution having a fixing ability means a processing solution containing a fixing agent among the processing solutions used in the desilvering process, and specifically, a fixing solution and a bleach-fixing solution. Specific examples of the desilvering process in the present invention are shown below, but the invention is not limited thereto. 1. Bleach-fix 2. Bleach-fixing 3. Bleach-bleach-fix 4. Bleach-fix-bleach-fix 5. Bleach-bleach-fix-fix 6. Bleach-bleach-fix-bleach-fix 7. Bleach-fix-fix 8. Bleach-fix-bleach-fix 9. Bleach-fix-fix 10. Bleach-fixing-bleaching Optionally, a water washing step may be provided between these treatments. In the present invention, from the viewpoint of exerting the effect remarkably, the above 2. Is most preferred.

In the present invention, the replenishing amount of the processing solution having a bleaching ability is set to 10 to 1000 ml per 1 m ² of the light-sensitive material, preferably 20 to 800 ml, and further 30
It is particularly preferable when the replenishment is reduced to 450 ml. The processing temperature of the processing solution having a bleaching ability in the present invention is 20 to 5
The temperature is 5 ° C, preferably 30 to 50 ° C. The processing time is preferably 10 seconds to 2 minutes, particularly 2
The range of 0 second to 1 minute and 30 seconds is preferable.

The processing solution having a bleaching ability containing the metal chelate compound according to the present invention contains the metal chelate compound as a bleaching agent, and also contains a chloride, a bromide, a rehalogenating agent for promoting the oxidation of silver. It is preferred to add a halide such as iodide. Further, an organic ligand which forms a sparingly soluble silver salt may be added instead of the halide. The halide is added as an alkali metal salt or ammonium salt, or a salt such as guanidine or amine. Specific examples include sodium bromide, ammonium bromide, potassium chloride, guanidine hydrochloride, potassium bromide, potassium chloride and the like. In the processing solution having the bleaching ability of the present invention, the amount of the rehalogenating agent is suitably 2 mol / l or less, and in the case of the bleaching solution, it is preferably 0.01 to 2.0 mol / l, more preferably 0 to 2.0 mol / l. 0.1 to 1.7 mol / l, particularly preferably 0.1 to 0.6 mol / l. In the bleach-fix solution, 0.001 to 2.
0 mol / liter is preferable, 0.001 to 1.0 mol / liter is more preferable, and 0.001 to 0.5 mol / liter.
Liters are particularly preferred.

The processing solution having a bleaching ability or its prebath according to the present invention contains a bleaching accelerator, a corrosion inhibitor for preventing corrosion of the processing bath, a buffer for maintaining the pH of the solution, a fluorescent whitening agent, and a defoaming agent. Agents and the like are added as needed. Regarding the bleaching accelerator, for example, US Pat. No. 3,893,858,
German Patent 1,290,821, British Patent 1,138,842, JP 53-95630.
And compounds having a mercapto group or a disulfide group described in Research Disclosure No. 17129 (July, 1978), JP-A-50-140129.
Thiazolidine derivatives described in Japanese Patent No. 3,7,7
Thiourea derivatives described in JP-A-06,561, iodides described in JP-A-58-16235, polyethylene oxides described in German Patent 2,748,430, and JP-B-45-8836. It is possible to use the polyamine compounds described in the publication. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. Particularly preferably British Patent No. 1,138,8
Mercapto compounds described in JP-A-42-190, JP-A-2-190856 are preferred.

The processing solution having a bleaching ability in the present invention contains an organic acid having two or more carboxyl groups (hereinafter,
It is preferable to include only a dicarboxylic acid compound). Examples of the dicarboxylic acid compound include saturated hydrocarbon compounds having two or more carboxyl groups in one molecule, unsaturated hydrocarbon compounds, aromatic hydrocarbon compounds, and heterocyclic compounds, and oxalic acid, malonic acid, succinic acid, Examples thereof include glutaric acid, adipic acid, maleic acid, fumaric acid, aspartic acid, citric acid, and 2,6-pyridinedicarboxylic acid. You may use these in combination of 2-4 types. In the treatment liquid having a bleaching ability in the present invention, an organic acid having a pKa of 2.0 to 5.5 such as acetic acid, glycolic acid, and propionic acid can be used in addition to the dicarboxylic acid compound. The organic acids may be used alone or in combination and are preferably contained as a buffer agent in an amount of 0.05 to 2.0 mol / liter, more preferably 0.1 to 1.5 mol / liter. . In the present invention, pKa represents the logarithm of the reciprocal of the acid dissociation constant, and shows the value obtained at 25 ° C. at an ionic strength of 0.1 mol / liter. pKa 2.0-
Specific examples of the organic acid of 5.5 include JP-A-3-1071.
No. 47, page 5, lower right column, second line to page 6, upper left column, tenth
The compounds mentioned in the rows are mentioned. In the present invention, an organic acid having a pKa of 2.0 to 5.5, such as acetic acid or propionic acid, which has a strong odor, other than dicarboxylic acid, has a concentration of 0.0 in a processing bath liquid (a processing liquid in direct contact with a photosensitive material).
~ 0.5 mol / l, especially 0.0-0.3 mol / l
The range of liter is preferable in terms of working environment.

The pH of the bleaching solution or the bleach-fixing solution of the present invention is 2.0 to 8.0, preferably 3.0 to 7.5. When bleaching or bleach-fixing is performed immediately after color development in a photographic material, the pH of the solution must be adjusted to prevent bleaching fog.
Is 7.0 or less, preferably 6.4 or less. Particularly in the case of a bleaching solution, it is preferably from 3.0 to 5.0.
When the pH is 2.0 or less, the metal chelate of the present invention tends to be unstable, and the pH is preferably 2.0 to 6.4. For a color print material, the pH is preferably in the range of 3 to 7. Any pH buffering agent can be used as long as it is not easily oxidized by the bleaching agent and has a buffering action in the above pH range. For example, the above-mentioned dicarboxylic acid compound, acetic acid, glycolic acid, lactic acid, propionic acid, butyric acid, malic acid, chloroacetic acid, levulinic acid, ureidopropionic acid, formic acid, pyruvic acid, isobutyric acid, pivalic acid, aminobutyric acid, valeric acid, iso Valeric acid, asparagine,
Alanine, arginine, ethionine, glycine, glutamine, cysteine, serine, methionine, leucine, histidine, benzoic acid, hydroxybenzoic acid, organic acids such as nicotinic acid, pyridine, dimethylpyrazole, 2-methyl-o-oxazoline, aminoacetonitrile, Examples thereof include organic bases such as imidazole. These buffers may be used in combination of two or more.

To adjust the pH of the processing solution having a bleaching ability to the above range, the above-mentioned acid and alkaline agent (for example, aqueous ammonia, KOH, NaOH, potassium carbonate, sodium carbonate, imidazole, monoethanolamine, diethanolamine) are used. You may use together. Among them, aqueous ammonia, KOH, NaOH, potassium carbonate and sodium carbonate are preferred.

Further, as a corrosion inhibitor, JP-A-3-3
It is preferable to use a nitrate as described in Japanese Patent No. 3847, and ammonium nitrate, sodium nitrate, potassium nitrate or the like is used. The addition amount is 0.01
~ 2.0 mol / liter, preferably 0.05-0.5
Mol / l.

[0192] In recent years, with increasing awareness of conservation of the global environment, efforts are being made to reduce nitrogen atoms emitted into the environment. From such a viewpoint, it is desired that the treatment liquid of the present invention does not substantially contain ammonium ions. In the present invention, the phrase "contains substantially no ammonium ion" means that the concentration of ammonium ion is 0.1.
1 mol / liter or less, preferably 0.0
8 mol / l or less, more preferably 0.01 mol / l
1 liter or less, particularly preferably a state in which it is not contained at all. In order to reduce the ammonium ion concentration in the range of the present invention, alkali metal ions and alkaline earth metal ions are preferable as alternative cation species, and alkali metal ions are particularly preferable, and lithium ion, sodium ion and potassium ion are particularly preferable. However, specifically, sodium salts and potassium salts of a ferric organic acid complex as a bleaching agent, potassium bromide as a rehalogenating agent in a processing solution having bleaching ability, sodium bromide, potassium nitrate, Sodium nitrate and the like. Further, as the alkaline agent used for pH adjustment, potassium hydroxide,
Sodium hydroxide, potassium carbonate, sodium carbonate and the like are preferred.

The processing solution having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance is kept extremely stable. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed using an ejector. When blowing air, it is preferable to release air into the liquid through a diffuser having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Eastman Kodak's Z-121, Using Process C-41 No. 3
Edition (1982), pages BL-1 to BL-2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is strengthened.
Page, upper right column, line 6-lower left column, line 2
Can be used as is.

The processing solution having bleaching ability of the present invention is
The overflow liquid used for the treatment is recovered, and after the components are added to correct the composition, the overflow liquid can be reused. Such a method of use is usually referred to as reproduction, but the present invention can also preferably perform such reproduction. For details of reproduction, see Fuji Photo Film Co., Ltd., Fuji Film Processing Manual, Fuji Color Negative Film, CN-16 processing (revised August 1990), page 39-
The matters described on page 40 are applicable. The kit for adjusting the processing solution having a bleaching ability of the present invention may be a liquid or a powder, but when ammonium salts are excluded, most of the raw materials are supplied as a powder, and since the hygroscopicity is also small,
Makes powder easier. From the viewpoint of reducing the amount of waste liquid, the regenerating kit is preferably a powder because it can be directly added without using excess water.

Regarding the regeneration of the processing solution having a bleaching ability,
In addition to the aeration mentioned above, "Basics of photographic engineering-silver halide photography-" (edited by the Photographic Society of Japan, published by Corona, 1979)
Year) can be used. Specifically, in addition to electrolytic regeneration, a method of regenerating a bleaching solution using bromic acid, zinc acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using a catalyst, bromite, ozone, or the like. No.
In the regeneration by electrolysis, the cathode and the anode are placed in the same bleaching bath, or the anode and the cathode are separated from each other by using a diaphragm to regenerate. And / or regenerating the fixing solution at the same time. The regeneration of the fixing solution and the bleach-fixing solution is carried out by electrolytic reduction of accumulated silver ions. Other,
It is also preferable to remove the accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance.

Ammonium thiosulfate has been generally used as a fixing agent in the desilvering process, but other known fixing agents such as mesoionic compounds, thioether compounds, thioureas, a large amount of iodide, It may be replaced with a hypo or the like. These are disclosed in JP-A-60-61749.
No. 60-147735, No. 64-21444, JP-A-1-201659
No. 1-210951, No. 2-44355, U.S. Pat.No. 4,378,42
No. 4 etc. For example, ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, guanidine thiosulfate, ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, dihydroxyethyl-thioether, 3,6-dithia-1,8-octanediol, imidazole and the like. No. Of these, thiosulfates and mesoions are preferred. Ammonium thiosulfate is preferable from the viewpoint of quick fixability, but sodium thiosulfate and mesoions are more preferable from the viewpoint of preventing the treatment liquid from substantially containing ammonium ions due to environmental problems as described above. Furthermore, by using two or more types of fixing agents in combination, it is possible to perform quicker fixing. For example, it is preferable to use the above-mentioned ammonium thiocyanate, imidazole, thiourea, thioether and the like in addition to ammonium thiosulfate and sodium thiosulfate. It is preferably added in the range of 01 to 100 mol%.

The amount of the fixing agent is the bleach-fixing solution or the fixing solution 1.
0.1 to 3.0 mol per liter, preferably 0.5 to
2.0 moles. The pH of the fixing solution depends on the type of the fixing agent, but is generally 3.0 to 9.0, and particularly when thiosulfate is used, 5.8 to 8.0 provides stable fixing performance. It is preferable above.

A preservative is added to the bleach-fixing solution or the fixing solution,
It is also possible to enhance the stability of the liquid over time. In the case of a bleach-fixing solution or a fixing solution containing thiosulfate, sulfite as a preservative, and / or bisulfite adduct of hydroxylamine, hydrazine, aldehyde (for example, bisulfite adduct of acetaldehyde, particularly preferred) The bisulfite adduct of aromatic aldehyde described in JP-A-3-158848 is effective.

Further, the bleach-fixing solution or the fixing solution containing the metal chelate compound of the present invention preferably contains at least one sulfinic acid and its salt. Preferred examples of sulfinic acid and its salt include JP-A-1-
230039, 1-224762, 1-231
051, No. 1-271748, No. 2-91643
No. 2, No. 2-251954, No. 2-251955, No. 3-55542, No. 3-158848, No. 4-51.
No. 237, No. 4-329539, U.S. Pat. No. 5,108.
No. 876, No. 4939072, EP No. 255722A.
Nos. 463639 and the like, and more preferably an optionally substituted arylsulfinic acid or a salt thereof, and further preferably an optionally substituted phenylsulfinic acid or a salt thereof. As the substituent, an alkyl group having 1 to 4 carbon atoms and 6 to 10 carbon atoms
Aryl group, carbamoyl group having 1 to 5 carbon atoms, alkoxycarbonyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 4 carbon atoms, sulfinic acid group, sulfonic acid group, carboxylic acid group, hydroxy group, halogen atom, etc. Is mentioned.

In the present invention, the effect is exhibited when the ammonium ion concentration in the processing solution having fixing ability is in the range of 0.0 to 2.0 mol / liter.
The range of 0 to 1.0 mol / liter is preferable, and the range of 0.0 to 0.5 mol / liter is more preferable. Particularly, a processing liquid having a fixing ability that does not contain ammonium ion is preferable. It is preferable to make the concentration of ammonium ions as low as possible even in the present situation where emission restrictions are imposed as an environmental pollution factor. The replenishing amount of the processing solution having fixing ability in the present invention is 10 per 1 m ² of the light-sensitive material.
~ 1000ml, but preferably 20-800
It is particularly preferable that the amount is 30 ml, and the supplemental amount is reduced to 30 to 500 ml. The processing temperature of the processing solution having fixing ability in the present invention is 20 to 55 ° C, preferably 30 to 50 ° C.
It is. The treatment time is preferably 10 seconds to 2 minutes, particularly 20 seconds to 1 minute 30 seconds, from the viewpoint of processing speed.

The processing solution having fixing ability may contain various fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like. Further, it is preferable to add a chelating agent such as various aminopolycarboxylic acids or organic phosphonic acids to the processing solution having a fixing ability for the purpose of stabilizing the processing solution. Preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, Cyclohexanediaminetetraacetic acid, 1,
2-Propylenediaminetetraacetic acid may be mentioned.
It is also preferable to add a buffering agent to the processing solution having fixing ability in order to keep the pH of the solution constant. For example, phosphates or imidazoles such as imidazole, 1-methyl-imidazole, 2-methyl-imidazole, 1-ethyl-imidazole, triethanolamine,
N-allylmorpholine, N-benzoylpiperazine and the like can be mentioned.

The total time for the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 10 seconds
It is 2 minutes, more preferably 10 seconds to 1 minute 30 seconds. The treatment temperature is 30 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In a preferred temperature range, the desilvering speed is improved,
In addition, the occurrence of stain after processing is effectively prevented.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. Specific examples of the method for strengthening stirring include a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and JP-A-62-1834.
A method of increasing the stirring effect using the rotating means of No. 61, and further moving the light-sensitive material while bringing the emulsion surface into contact with the wiper blade provided in the liquid to make the emulsion surface turbulent, thereby further improving the stirring effect. Examples thereof include a method for improving the method and a method for increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic processor used in the present invention is disclosed in JP-A-60-191257, JP-A-60-191258, and JP-A-60-19125.
It is preferable to have the photosensitive material conveying means described in No. 9. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The color developer used in the development processing of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3 -Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-
β-methanesulfonamide ethylaniline, 3-methyl-4
-Amino-N-ethyl-β-methoxyethylaniline, 4-
Amino-3-methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl- N-
Ethyl-N- (2-hydroxypropyl) aniline, 4-amino
-3-Ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N -Methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-
Methyl-N-methyl-N- (4-hydroxybutyl) aniline,
4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-
Hydroxybutyl) aniline, 4-amino-3-ethyl-N-
Ethyl-N- (3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-methyl-N- (5-
Hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, N-bis ( Five
-Hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline,
4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 3-methyl-4-amino-N-ethyl-N-β-
Methanesulfonamidoethylaniline and their hydrochlorides, p-toluenesulfonates or sulfates are preferred, and further 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3 -Methyl-N-ethyl
Preferred are -N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline and their hydrochlorides, p-toluenesulphonates or sulphates. These compounds can be used in combination of two or more depending on the purpose.

The amount of the aromatic primary amine developing agent used is preferably 0.0002 mol to 0.2 mol, and more preferably 0.001 mol to 0.1 mol per liter of the color developing solution.
It is 1 mol.

In the present invention, it is most preferable that the color developing solution contains substantially no hydroxylamine from the viewpoint that the effects of the present invention can be remarkably exhibited. In the present invention, substantially free of hydroxylamine means that the concentration of hydroxylamine is 0.01 mol / liter or less, preferably 0.005 mol / liter or less, and more preferably 0.001 mol / liter. Less than or equal to 1 liter, particularly preferably not contained at all. As a compound instead of hydroxylamine, a hydroxylamine derivative having a substituent such as an alkyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group is preferable, and specifically, N, N-di (sulfoethyl) hydroxylamine, monomethyl Hydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl) hydroxylamine are preferred. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferred.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt,
It generally contains a development inhibitor or an antifoggant such as a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. If necessary, hydroxylamine, diethylhydroxylamine, hydroxylamines represented by the general formula (I) of JP-A-3-144446, sulfite, N,
Hydrazines such as N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, Development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos. Various chelating agents represented by carboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphospho Acid, nitrilo -N, N, N-
Trimethylenephosphonic acid, ethylenediamine-N, N, N, N-
Tetramethylenephosphonic acid, ethylenediamine-di (o
-Hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

The processing temperature of the color developing solution in the present invention is 20 to 55 ° C, preferably 30 to 50 ° C. The treatment time is 10 seconds to 3 minutes and 30 seconds, preferably 20 seconds to 2 minutes and 30 seconds, and more preferably 3 from the viewpoint of processing speed.
It is 0 second to 1 minute and 30 seconds.

When the reversing process is carried out, black and white development is usually carried out and then color development is carried out. This black-and-white developer contains dihydroxybenzenes such as hydroquinone and hydroquinone monosulfonate, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, or N. Known black-and-white developing agents such as aminophenols such as -methyl-p-aminophenol can be used alone or in combination. The pH of these color developing solution and black and white developing solution is 9 to
It is generally 12. The replenishing amount of these developing solutions is preferably 50 to 600 ml, and more preferably 80 to 300 ml per square meter of the light-sensitive material. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

The contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. Is. As a method of reducing the aperture ratio in this manner, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, 63-216050 can be mentioned. Further, a method of contacting a liquid covering the processing liquid surface, such as liquid paraffin, or a low-oxidizing and / or non-oxidizing gas with the processing liquid surface may also be used. The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The desilvering process of the present invention is preferably carried out immediately after color development, but in the case of reversal process, it is carried out through an adjusting bath (a bleaching promoting bath or a prebleaching bath may be used). Is common. It is preferable to use an adjustment stabilizer containing these image stabilizers in these adjustment baths because the image stability is improved. As the adjustment liquid, other than the image stabilizer,
Aminopolycarboxylic acid chelating agents such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-propylenediaminetetraacetic acid, cyclohexanediaminetetraacetic acid, sodium sulfite, sulfite salts such as ammonium sulfite and thioglycerin, aminoethanethiol,
Various bleaching accelerators described later such as sulfoethanethiol can be contained. For the purpose of preventing scum, sorbitan esters of ethylene oxide-substituted fatty acids described in U.S. Pat. No. 4,839,262, U.S. Pat. No. 4,059,446 and Research Disclosure, Vol. It is preferable to contain the described polyoxyethylene compound or the like. These compounds are used in an amount of 0.1
It can be used in the range of g to 20 g, but is preferably in the range of 1 g to 5 g. The pH of the adjusting bath is usually 3 to
It is used in the range of 11, but is preferably 4 to 9, and more preferably 4.5 to 7. Processing time in the conditioning bath is 2
It is preferably 0 seconds to 5 minutes. More preferably 20
Seconds to 100 seconds, most preferably 20 seconds to 60 seconds. Moreover, the replenishment amount of the adjusting bath is 3 per 1 m ² of the light-sensitive material.
0 ml to 3000 ml is preferable, but especially 50 ml to 1500 ml
It is preferably ml. The treatment temperature of the conditioning bath is 20 ℃
50 ° C. is preferable, but 30 ° C. to 40 ° C. is particularly preferable.

In the present invention, after desilvering processing, washing and / or stabilizing steps are carried out. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in the Journal of the Society of Motion Pictu
re and Television Engineers Volume 64, P. 248 ~ 253 (1
May 955)).
According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, such a problem is a solution,
The method of reducing calcium and magnesium ions described in JP-A-62-288,838 can be used very effectively. Also, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antibacterial and fungicide" (1986
Year) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Antimicrobial and Antifungal Society, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) A bactericide can also be used.

Rinsing water in the processing of the light-sensitive material of the present invention
The pH is 3-9, preferably 4-8. From the viewpoint of quickness, the washing water temperature and washing time should be 5 to 50 seconds at 15 to 50 ° C.
A range of 1 minute, preferably 5 to 40 seconds at 25 to 45 ° C is selected. In the stabilizing solution, compounds that stabilize the dye image, for example, benzaldehydes such as formalin and m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and its derivatives,
Hexahydrotriazine and its derivatives, dimethylol urea, N-methylol compounds such as N-methylol pyrazole, organic acids, pH buffering agents and the like are included. The preferable addition amount of these compounds is 0.0 per 1 liter of the stabilizing solution.
Although it is from 0.1 to 0.02 mol, it is preferable that the concentration of free formaldehyde in the stabilizing solution is lower, because formaldehyde gas is less scattered. From this point of view, examples of the dye image stabilizer include m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolpyrazole, N-methylolazoles described in JP-A-4-270344, N, N'-bis (1 , 2,4-Triazol-1-ylmethyl) piperazine, etc.
Azolylmethylamines described in No. 53 are preferable. In particular, JP-A-4-359249 (corresponding to European Patent Publication No. 51
9190A2) and the combination of an azole such as 1,2,4-triazole and an azolylmethylamine such as 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine and a derivative thereof. , High image stability and low formaldehyde vapor pressure are preferable. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, film hardeners, US Pat.
No. 583, an alkanolamine, and a preservative that can be contained in the fixing solution or the bleach-fixing solution, for example,
It is also preferable to contain the sulfinic acid compound described in JP-A No. 1-231051.

Further, in the case where the desilvering process of the present invention has a one-tank constitution of a bleach-fixing solution, it is preferable that the bleach-fixing process is followed by a direct stabilizing process without substantially washing with water. . In the present invention, performing the stabilization treatment step directly without passing through the washing step means that the bleach-fixing solution brought into the stabilization treatment tank (the tank closest to the bleach-fixing tank when it is composed of two or more tanks). The capacity is 1% or more, preferably 5% or more, and more preferably 10% or more with respect to that of the stabilizing solution. If the concentration of the bleach-fixing solution in the stabilizing treatment tank does not fall below 1%, an extremely short time rinsing treatment by a single-current or multi-current countercurrent method, auxiliary water washing, and water washing accelerating bath are performed. Good. In such stabilization treatment, JP-A-57-8543, JP-A-58-14834, and JP-A-60-220.
All known methods described in No. 345 can be used.

The pH of the stabilizing solution in the processing of the light-sensitive material of the present invention is preferably in the range of 4.0 to 5.5, more preferably 4.
It is in the range of 2 to 5.3, and the effect of the present invention becomes remarkable in this range. Such a stabilizing solution preferably contains an organic acid having two or more carboxyl groups (hereinafter, simply referred to as a dicarboxylic acid compound). As the dicarboxylic acid compound, a saturated hydrocarbon compound having two or more carboxyl groups in one molecule, an unsaturated hydrocarbon compound,
Aromatic hydrocarbon compounds, heterocyclic compounds, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid,
Maleic acid, fumaric acid, aspartic acid, citric acid,
2,6-pyridinedicarboxylic acid and the like can be mentioned. You may use these in combination of 2-4 types. The stabilizing solution contains acetic acid, glycolic acid, a dicarboxylic acid compound,
An organic acid having a pKa of 2.0 to 5.5 such as propionic acid can be used. The organic acids may be used alone or in combination, and the content of the buffering agent is preferably 0.001 to 0.2 mol / liter, more preferably 0.005 to 0.15 mol / liter. In the present invention, pKa represents the logarithm of the reciprocal of the acid dissociation constant, and shows the value obtained at 25 ° C. at an ionic strength of 0.1 mol / liter. pKa2.
Specific examples of the organic acid of 0 to 5.5 are disclosed in JP-A-3-10.
The compounds described in JP-A 7147, page 5, lower right column, line 2 to page 6, upper left column, line 10 can be mentioned. In the present invention, an organic acid having a pKa of 2.0 to 5.5 such as acetic acid or propionic acid having a strong odor other than dicarboxylic acid has a concentration of 0.0 in the solution of the processing bath (processing solution which the photosensitive material directly contacts).
From the viewpoint of working environment, it is preferably in the range of .about.0.2 mol / liter, particularly 0.0 to 0.15 mol / liter.

To adjust the pH of the stabilizing solution to the above range, the acid and the alkaline agent (for example, ammonia water, K
OH, NaOH, potassium carbonate, sodium carbonate, imidazole, monoethanolamine, diethanolamine) may be used in combination. Among them, ammonia water and KO
H, NaOH, potassium carbonate and sodium carbonate are preferred.

In the stabilizing solution, compounds that stabilize the dye image, such as formalin, benzaldehydes such as m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, Examples include N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffering agents. The preferable addition amount of these compounds is from 0.001 to 0.02 mol per liter of the stabilizing solution. However, the lower the concentration of free formaldehyde in the stabilizing solution, the less the formaldehyde gas is scattered. From these viewpoints, examples of the dye image stabilizer include N-methylolazoles such as m-hydroxybenzaldehyde, hexamethylenetetramine and N-methylolpyrazole described in JP-A-4-270344, and N, N'-bis (1 4,3,4-triazol-1-ylmethyl) piperazine and the like.
Azolylmethylamines described in 13753 are preferred. In particular, azoles such as 1,2,4-triazole and 1,4-bis (1,2,4) described in JP-A-4-359249 (corresponding to EP-A-519190A2).
A combination of azolylmethylamine and its derivative such as (-triazol-1-ylmethyl) piperazine is preferable because of high image stability and low formaldehyde vapor pressure. Further, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, a fluorescent brightener, a hardener, and US Pat.
No. 86,583, and a preservative which can be contained in the above-mentioned fixing solution or bleach-fixing solution, for example, a sulfinic acid compound described in JP-A-1-231105 is also preferable. .

Various surfactants can be contained in the washing water and the stabilizing solution in order to prevent unevenness of water droplets during drying of the processed light-sensitive material. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. It is also preferable to use a silicon surfactant having a high defoaming effect.

It is preferable to add various chelating agents to the washing water and the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N'-trimethylenephosphonic acid, diethylenetriamine-N, N,
Organic phosphonic acids such as N ', N'-tetramethylenephosphonic acid, and a hydrolyzate of a maleic anhydride polymer described in European Patent 345,172A1 can be mentioned.

The overflow solution accompanying the above washing with water and / or replenishment of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation,
In order to correct the concentration by evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenisher. There is no particular limitation on a specific method for performing water replenishment. Among them, a monitor water tank separate from the bleaching tank described in JP-A Nos. 1-254959 and 1-254960 is installed, and water in the monitor water tank is provided. The amount of evaporation of water is calculated, the amount of evaporation of water in the bleaching tank is calculated from the amount of evaporation of water, and water is supplied to the bleaching tank in proportion to the amount of evaporation.
Nos. 3,249,644, 3,249,645, and 3,249,646, the evaporation correction method using a liquid level sensor and an overflow sensor are preferable.
Tap water may be used as water for correcting the evaporation of each processing solution, but it is preferable to use deionized water or sterilized water which is preferably used in the above-mentioned washing step.

The automatic processor used in the present invention is disclosed in
It is preferable to have the photosensitive material transporting means described in 60-191257, 60-191258, and 60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to.

The supply form of the treating agent used in the present invention is as follows:
It may be in any form, such as a liquid preparation in the form of a liquid used or a concentrated form, or granules, powders, tablets, pastes, and emulsions. As an example of such a treating agent, JP-A-63-1
7453 discloses a liquid agent contained in a container having low oxygen permeability,
19655, 4-230748, vacuum-packed powders or granules, 4-221951, granules containing a water-soluble polymer,
JP-A-51-61837 and JP-A-6-102628 have tablets and special tables
Discloses a paste-like treating agent, which can be preferably used, but from the viewpoint of simplicity at the time of use,
It is preferable to use a liquid which has been prepared in advance in a concentration at the state of use. Polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon and the like are used alone or as a composite material in a container for containing these treatment agents. These are selected according to the required level of oxygen permeability. For an easily oxidizable liquid such as a color developing solution, a material having low oxygen permeability is preferable, and specifically, a polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials are used in containers having a thickness of 500 to 1500 μm, and preferably have an oxygen permeability of 20 ml / m ² · 24 hrs · atm or less.

In the present invention, each processing solution can be commonly used for processing two or more kinds of photosensitive materials. For example,
By processing the color negative film and the color paper using the same processing liquid, the cost of the processing machine can be reduced and the processing can be simplified.

[0225]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 101 as a multilayer color photosensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.30 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS- 1 0.15 HBS-2 0.02

Second layer (intermediate layer) ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver chlorobromide emulsion A Silver 0.25 Silver chlorobromide emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Chlorobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver chlorobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh layer (low-sensitivity green-sensitive emulsion layer) Silver chlorobromide emulsion E Silver 0.15 Silver chlorobromide emulsion F Silver 0.10 Silver chlorobromide emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Chlorobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.88

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver chlorobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.00

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.70

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver chlorobromide emulsion J Silver 0.09 Silver chlorobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.73 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.32 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver chlorobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

Thirteenth layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.2

14th layer (second protective layer) Silver chloride emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S- 1 0.20 Gelatin 0.70

Further, in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property, each layer may be provided with W-1 to W-3, B-4 to B-. 6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0242]

[Table 1]

In Table 1, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
Reduction sensitization was performed using thiourea dioxide and thiosulfonic acid during the preparation of the particles. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer. (3) Tabular grains are prepared according to the examples of Japanese Patent Application No. 5-96250.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of an aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the fine dye particles were 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
Dispersed by a dispersion method. The average particle size was 0.06 μm.

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Sample 101 described above was cut into a width of 35 mm and photographed with a camera. The following processing steps and treatment liquids were used 5 times a day (24 shots / 35 mm width 1.1 m equivalent per one). ) Each for about 4 months. A cine type automatic developing machine was used for each treatment, and the bleaching solution was changed in the bleaching agent used as shown in Table 2, and the bleaching solution was sequentially exchanged for each to carry out the running treatment. (Processing step) Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 40 seconds 45.0 ℃ 260 ml 2.5 liter Bleach 20 seconds 45.0 ℃ 130 ml 1.5 liter Fixed (1) 20 seconds 40.0 ℃ − 1.5 liter Fixed (2 ) 20 seconds 40.0 ℃ 400 ml 1.5 liters Water wash 20 seconds 40.0 ℃ 800 ml 1.5 liter Stability (1) 20 seconds 40.0 ℃ − 1.5 liter Stability (2) 20 seconds 40.0 ℃ 130 ml 1.5 liter Dry 30 s 65 ℃ * The replenishing amount is per 1 m ² of the light-sensitive material, the fixing solution and the stabilizing solution are in the countercurrent system from (2) to (1), and the overflow solution of washing water is all introduced into the fixing bath. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the fixing process, the amount of fixing solution brought into the washing process and the amount of washing solution brought into the stabilizing process are 1 m ² of the light-sensitive material.
40 ml, 33 ml, 38 ml,
It was 65 ml. The crossover time is 3 seconds in each case, and this time is included in the processing time of the previous step. As evaporation correction in each tank, JP-A-3-28004
As described in No. 2, the temperature and humidity of the outside air of the processor were detected by a thermo-hygrometer, and the evaporation amount was calculated and corrected. As the water for evaporation correction, the following ion-exchanged water for washing water was used.

The composition of the treatment liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 4.0 4.0 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 0.5 Sodium bicarbonate 1.8 1.8 Sodium sulfite 4.0 6.7 Potassium carbonate 40.0 40.0 Potassium bromide 0.01-Potassium chloride 1.6-Hydroxylamine sulfate 4.8 6.8 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.0 17.0 Water was added to 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.30

(Bleaching solution) Tank solution (g) Replenishing solution (g) Ferric complex salt shown in Table 0.35 mol 0.46 mol Ammonium bromide 70.0 91.0 Ammonium nitrate 14.0 18.2 Succinic acid 60.0 78.0 Glutaric acid 20.0 26.0 Adipic acid 10.0 13.0 Malein Acid 20.0 26.0 Add water 1.0 liter 1.0 liter pH (adjusted with ammonia water) 4.4 4.0

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / l) 280 ml 840 ml Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water 1.0 liter 1.0 liter pH (Prepared with aqueous ammonia and acetic acid) 7.4 7.4

(Washing Water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
Per liter or less, followed by 20 mg / liter of sodium diisocyanurate and 150 mg of sodium sulfate.
mg / l was added. The pH of this solution is 6.5 to 7.
5 range.

(Stabilizing Solution) Common to Tank Solution and Replenishing Solution (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

After the completion of the running process, the condition of the tank wall of the bleaching tank and the state of the transport roller were observed.

The results are shown in Table 2.

[0270]

[Table 2]

From the results shown in Table 2, the combination of the light-sensitive material and the processing solution according to the present invention makes it possible to carry out maintenance-free operation even in a long-running running process, and quick desilvering and processing stability. It can be seen that both improvements were achieved. Although it is known that desensitization can be speeded up by using the light-sensitive material of the aspect of the present invention, the processing stability in the off-season deteriorates in combination with the bleaching solution of the aspect of the present invention. It was an unexpected effect that I was able to suppress the.

Example 2 (1) Support Material and the Like Each support used in this example was prepared by the following method. PEN: 100 parts by weight of polyethylene-2,6-naphthalate polymer and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy) as an ultraviolet absorber were dried,
After melting at 300 ℃, extrude from T-die and at 140 ℃
The film is longitudinally stretched 3.3 times, then transversely stretched 3.3 times at 130 ° C, and heat-set at 250 ° C for 6 seconds to obtain a thickness of 90 μm.
I got the PEN film. This PEN film contains blue dye, magenta dye and yellow dye (I-1, I-4, I-6, I-24, I-26, I- 27, I
I-5) was added in an appropriate amount. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support that was not easily curled. -TAC: methylene chloride / methanol = 82/8 wt.
Ratio, TAC concentration 13%, plasticizer TPP / BDP = 2/1
(Here, TPP; triphenyl phosphate, BD
P; biphenyl diphenyl phosphate) 15 wt%
Produced by the band method described above.

(2) Coating of undercoat layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment, and glow discharge treatment on both sides, and then PE was applied to each surface.
N support is gelatin 0.1 g / m ² , sodium α-sulfodi-
2-ethylhexyl succinate 0.01 g / m ² , salicylic acid
0.04 g / m ² , p-chlorophenol 0.2 g / m ² , (CH ₂ = CHSO ₂
CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.012 g / m ² , polyamide-epichlorohydrin polycondensate 0.02 g / m ² undercoat liquid, TAC support gelatin 0.2 g / m ² , salicylic acid 0.1 g / m ² , methanol 15 ml /
An undercoat liquid of m ² , acetone 85 ml / m ² and formaldehyde 0.01 g / m ² was applied (10 cc / m ² , using a bar coater), and the undercoat layer was provided on the high temperature surface side during stretching. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).

(3) Coating of Back Layer An antistatic layer having the following composition, a magnetic recording layer and a sliding layer were coated as a back layer on one surface of the above-mentioned support after undercoating.

(3-1) Coating of antistatic layer A dispersion of fine particle powder having a specific resistance of 5 Ω · cm of tin oxide-antimony oxide composite having an average particle size of 0.005 μm (secondary agglomerated particle size of about 0.08 μm) 0.2 g / m ² , gelatin 0.05 g / m ² , (C
H ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 1
0) Oxyethylene-p-nonylphenol 0.005 g / m ²
And resorcinol. (3-2) Coating of magnetic recording layer 3-Poly (degree of polymerization 15) Cobalt-γ-iron oxide coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g , Long axis 0.14μm, single axis 0.03μm, saturation magnetization 89emu / g, Fe ^{+ 2} / Fe ⁺³ = 6/94, the surface is treated with aluminum oxide silicon oxide at 2% by weight of iron oxide) 0.06g / m ² of diacetyl cellulose 1.2 g / m ² (dispersion of the iron oxide was carried out using an open kneader and a sand _{mill), C 2 H 5 C (} CH 2 OCONH-C 6 H 3 (CH 3) NCO) as a curing agent ₃
0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone, cyclohexanone as a solvent,
A magnetic recording layer having a thickness of 1.2 μm was obtained. Abrasive aluminum oxide (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) as matting agents, respectively
It was added to 10 mg / m ² . Drying was carried out at 115 ° C for 6 minutes.
° C). X- write saturation magnetization moment of the magnetic recording layer of the D color density increment of about 0.1 of ^B, also the magnetic recording layer is 4.2 emu / g, coercive force 7.3 × 10 ⁴ A / m, the squareness ratio in (blue filter) Was 65%.

(3-3) Preparation of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ C
OOC ₄₀ H ₈₁ (compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H
(Compound b, 9 mg / m ² ) mixture was applied. In addition, this mixture is xylene / propylene monomethyl ether (1/1)
The mixture was melted at 105 ° C. in water, and dispersed by pouring into propylene monomethyl ether (10-fold amount) at room temperature, and then dispersed in acetone (average particle size: 0.01 μm) and then added. As a matting agent, silica particles (0.3 μm) and abrasive 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (aluminum oxide (0.15 μm) coated with 15% by weight) are each 15 mg / m ² . And dried at 115.
C. for 6 minutes (115 ° C. for all rollers and conveyors in the drying zone). The sliding layer had a dynamic friction coefficient of 0.06 (stainless steel hard ball of 5 mmφ, load of 100 g, speed of 6 cm / min), a static friction coefficient of 0.07 (clip method), and a dynamic friction coefficient of 0.12 between the emulsion surface and the sliding layer which will be described later. .

(4) Preparation of Photosensitive Layer Next, the photosensitive layer described in Example 1 was coated on the side opposite to the back layer obtained above.

The photosensitive layer shown in (5) was coated on the two types of supports prepared by the above method to prepare a photosensitive material. P
The sample with EN support was designated as sample 201, and the sample with TAC support was designated as sample 202.

Samples 201 to 202 described above are 24 mm
The photosensitive material is cut to a width of 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm 0.7 mm from one side in the length direction of the photosensitive material. The two sets were prepared at intervals of 32 mm, and were produced in US Pat.
No. 6,887. 1 to FIG. 7 was housed in a plastic film cartridge.

These samples were photographed with a camera, and subjected to running treatment for 5 months per day (corresponding to 24 mm width 1.6 m) with the following processing steps and processing solutions for about 3 months. Each processing was carried out by using a cine type automatic developing machine, the bleach-fixing solution was changed in the bleaching agent used as shown in Table 3, and the bleaching-fixing solution was sequentially replaced for each running processing.

The details of the processing executed are shown below. The bleach-fix solution was subjected to in-line silver recovery with a silver recovery device.
The silver recovery device is a small electrolytic silver recovery device with an anode of carbon and a cathode of stainless steel with a current density of 0.5.
Used at A / dm ² . Specifically, JP-A-6-17530
The one described in FIG. 1 of Japanese Patent No. 5 was used. However, no regenerant was used. In other words, the overflow 21 of the bleach-fixing tank 20 is directly connected to the silver recovery device 22, and 100 ml of the overflow per minute is filtered by the pump 23 by the pump 24.
It is returned to the original bleach-fixing tank 20 through. Silver recovery device 2
The overflow 25 from 2 collects 300 ml per 1 liter of overflow into the regenerating tank 26, and blows air for about 2 hours at the time when the collected amount becomes 1 liter, and then into the replenishing tank 30 of the bleach-fixer by the pump 29. Sent. The remaining liquid (100 ml) is discharged as waste liquid 27
I let it.

Treatment process (Process) (Treatment time) (Treatment temperature) (Replenishment amount) ^{* 1} (Tank capacity / liter) Color development 40 seconds 45 ℃ 260ml 2.5 Bleach fixing 40 seconds 40 ℃ 130ml 2.5 Water wash 20 seconds 40.0 ℃ 400ml 2.0 Stability (1) 20 sec 40.0 ℃ − 2.0 Stability (2) 20 sec 40.0 ℃ 400ml 2.0 Dry 50 sec 65 ℃ * 1 Replenishment amount per 1 m ² of photosensitive material Stabilizer is from (2) It is a countercurrent method to (1). The overflow liquid of the washing water was discharged as waste liquid. The crossover time is 3 seconds in each case, and this time is included in the processing time of the previous step. As described in JP-A-3-280042, the temperature and humidity of the outside air of the processor were detected by a thermo-hygrometer in each tank as the evaporation correction, and the evaporation amount was calculated and corrected.
As the water for evaporation correction, the following ion-exchanged water for washing water was used. The composition of the treatment liquid is shown below.

(Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 4.0 4.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.0 Sodium bicarbonate 1.8 1.8 Sodium sulfite 4.0 6.7 Potassium carbonate 40.0 40.0 Bromide Potassium 0.01-Potassium chloride 1.6-Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 13.2 17.2 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.0 17.0 1.0 liter by adding water 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.30

(Bleach-fixing solution) Tank solution (g) Replenishing solution (g) Ferric complex salt shown in Table 0.16 mol 0.210 mol Ethylenediaminetetraacetic acid 6.0 7.9 Succinic acid 12.0 15.6 Ammonium sulfite 20 50 Ammonium thiosulfate aqueous solution (700 g / liter) ) 300 390 Para-aminobenzenesulfinic acid 5.0 15 Ammonium iodide 1.0 1.3 Add water 1.0 liter 1.0 liter pH (prepared with ammonia water and nitric acid) 6.0 5.6

(Washing Water) Common to mother liquor and replenisher The same composition as the washing water of Example 1 of the present application.

(Stabilizer) Mother liquor and replenisher common (unit: g) Succinic acid 0.2 p-Toluenesulfinic acid sodium 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 1,2-benzisothiazoline- 3-one 0.05 Sodium chlorinated isocyanurate 0.02 Add water 1.0 liter pH (adjust with nitric acid and ammonia water) 5.0

After the running treatment was completed, the condition of the wall surface of the washing tank, the transport roller and the circulation filter was observed.

The results are shown in Table 3.

[0289]

[Table 3]

From the results of Table 3, good results can be obtained in the present invention even if the processing steps are changed. Therefore, even if the desilvering time was further shortened by the one-tank constitution of the bleach-fixing solution, good results were obtained in the present invention. Further, Experiment Nos. 2 to 4 are all embodiments of the present invention, but in the rapid desilvering process of the one-bath constitution of the bleach-fixing solution, the conventional light-sensitive material may not have sufficient processing stability. . However, it is unexpected that the use of the magnetic recording layer and the support, which is a preferred embodiment of the present invention, can further reduce the frequency of replacement of the circulation filter.

Example 3 The sample 201 described in Example 2 of the present application was cut and processed in the same manner as in Example 2 and photographed with a camera, and the following processing steps and processing liquids were used three times a day (one 24 mm width 1 (Corresponding to .6 m) for about 4 months. A cine type automatic developing machine was used for each processing, and the preservatives used for the color developing solution were changed as shown in Table 4, and each of them was sequentially replaced and the running processing was performed.

Details of the processing executed are shown below. The bleach-fix solution was subjected to in-line silver recovery as in Example 2. For the stabilization treatment, a countercurrent cascade was carried out by using a 5-stage multi-chamber stabilizer arranged horizontally. Specifically, JP-A-5-6
The one described in FIG. 1 of the 6540 specification was used. A schematic diagram of the processor is shown in FIG. 2 of JP-A-6-175305. However, the overflow solution of the first stabilizing solution was discharged as a waste solution without being cascaded to the bleach-fixing tank of the previous bath, and the reverse osmosis membrane (RO) device between the fourth stability and the fifth stability was not installed.

The processing steps are shown below.

Treatment process (Process) (Treatment time) (Treatment temperature) (Replenishment amount) ^{* 1} (Tank capacity / liter) Color development 40 seconds 45 ℃ 260ml 2.5 Bleach fixing 40 seconds 40 ℃ 260ml 2.5 Stable (1) 15 40 ℃ − 0.8 Stable (2) 15 s 40 ℃ − 0.8 Stable (3) 15 s 40 ℃ − 0.8 Stable (4) 15 s 40 ℃ − 0.8 Stable (5) 15 s 40 ℃ 260 ml 0.8 Dry 50 s 70 ℃ − − * 1 Replenishment amount per 1 m ² of light-sensitive material

The composition of the treatment liquid is shown below.

(Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 4.0 4.0 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 0.5 Sodium bicarbonate 1.8 1.8 Sodium sulfite 4.0 6.7 Potassium carbonate 40.0 40.0 Potassium bromide 0.01 − Potassium chloride 1.6 − Preservatives listed in Table 4 0.06 mol 0.85 mol 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.0 17.0 1.0 liter by adding water 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.30

(Bleach-fixing solution) Tank solution (g) Replenishing solution (g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 16.0 19.0 (I-22) ferric complex salt 0.10 mol 0.12 mol Ethylenediaminetetraacetic acid 6.0 6.9 Amber Acid 12.0 14.0 Ammonium sulfite 20 40 Ammonium thiosulfate aqueous solution (700 g / liter) 300 345 Para-aminobenzenesulfinic acid 5.0 15 Ammonium iodide 1.0 1.1 Water is added 1.0 liter 1.0 liter pH (prepared with ammonia water and nitric acid) 6.0 5.8

(Stabilizer) Mother liquor and replenisher common (unit: g) Succinic acid 1.0 Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 1,2-Benzisothiazoline- 3-one 0.05 Sodium chlorinated isocyanurate 0.02 Add water 1.0 liter pH (adjusted with nitric acid and ammonia water) 4.8

After the running treatment was completed, the state of the wall surface of the stabilizing tank, the transport roller and the circulation filter was observed.

The results are shown in Table 4.

[0301]

[Table 4]

Although all of the present embodiments are aspects of the present invention, the result of the present invention is that the use of hydroxylamine in the color developing solution makes it possible to reduce the replenishment rate and to achieve maintenance-free operation even in a very quiet process. I got it.

[0303]

According to the structure of the present invention, maintenance-free operation is possible even in a low-replenishment and rapid processing, which is a continuous continuous operation.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 1/035 G03C 1/035 CH 1/79 1/79 1/81 1/81 7/00 510 7/00 510 530 530 7/407 7/407

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the emulsion layer of the light-sensitive material has a silver chloride content of 50 having a (100) plane as a main plane. A metal chelate of a compound represented by the following general formula (I) which contains mol% or more of tabular silver halide grains and is subjected to color development after imagewise exposure of the silver halide color photographic light-sensitive material. A method of processing a silver halide color photographic light-sensitive material, which comprises processing with a processing solution having a bleaching ability containing at least one compound. General formula (I) (In the formula, R ₁ represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. R ₂ represents a hydrogen atom, an aliphatic hydrocarbon group,
Represents an aryl group or a heterocyclic group. L ₁ , L ₂ , L
₃ , L ₄ and L ₅ each represent an alkylene group.
m and n each represent 0 or 1. W ¹ and W ² each represent an alkylene group, an arylene group, an aralkylene group or a divalent nitrogen-containing heterocyclic group. D represents a single bond, -O-, -S- or -N (Rw)-. R
w represents a hydrogen atom, an aliphatic hydrocarbon group or an aryl group. v represents an integer of 0 to 3, and w represents an integer of 1 to 3. M ₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation. ) 2. The photosensitive material has a magnetic recording layer, the support has a thickness of 50 to 150 μm, and the glass transition temperature is 50 to 200.
A polyethylene aromatic dicarboxylate-based polyester at a temperature of 40 ° C, which is heat-treated at a temperature of 40 ° C or higher and a glass transition temperature or lower for 0.1 to 1500 hours before the undercoat layer is applied or after the undercoat layer is applied and before the emulsion layer is applied. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein 3. The method for processing a silver halide color photographic light-sensitive material according to claim 2, wherein the color developing solution contains substantially no hydroxylamine.