JPH08328222A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To restrain occurrence of yellow stains of photosensitive material after continuous processing and occurrence of magenta stains after having been preserved in wet and hot circumstances and uneven processing by incorporating a specified compound in a processing solution. CONSTITUTION: A processing solution having a bleaching power contains at least one kind of metal chelate compound represented by formula I or II and the photosensitive material is processed by impinging the jet of the processing solution to the emulsion surface of the photosensitive material in the bath of this processing solution. In the formulae I and II, Y1 is a nonmetallic atomic group necessary to form an aromatic hydrocarbon ring or heterocyclic group; R1 is a substituent; (n) is an integer of 0-4; X1 is H atom or a -L1 -A2 group; X3 is H atom or a -L4 -A4 group; each of L1 , L3 , and L4 is an alkylene or arylene group; W1 is a divalent bonding group; and each of A1 -A5 is a carboxy, sulfo, or phosphono group or its salt, or a hydroxy or hydroxyalkyl group or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material (hereinafter, also simply referred to as a light-sensitive material), more specifically, improvement of desilvering property and / or long-term The present invention relates to a treatment method which is excellent in stability of continuous treatment for a period, and enables reduction of treatment time.

[Prior art]

In recent years, the photographing system for silver halide color photographic light-sensitive materials is so-called "photographing" Super80.
The widespread use of high-sensitivity film with a lens, represented by 0 ”, has made it extremely convenient and allows you to easily enjoy high-quality photos. However, the processing system is faster than the convenience of the shooting system. The quality has not reached the requirements of users, and further speeding up of the processing, especially shortening of the desilvering process, which occupies almost half of the processing time, has become an extremely important issue.

Generally, the processing of a silver halide color photographic light-sensitive material basically comprises a color development step and a desilvering step.
In the desilvering process, the developed silver produced in the color development process is oxidized (bleached) to a silver salt by a bleaching agent having an oxidizing action, and further removed from the photosensitive layer by a fixing agent that forms soluble silver together with unused silver halide. Be done (fixed).

Conventionally, as means for accelerating the desilvering process,
A bleach-fixing solution containing a ferric aminopolycarboxylic acid complex salt and thiosulfate described in German Patent 866,605 is known. This is preferable from the viewpoint of downsizing of the apparatus, because the number of processing baths can be reduced. However, originally, the oxidizing power (bleaching power)
Since a ferric aminopolycarboxylic acid ferric complex salt having a weak property is coexistent with a thiosulfate having a reducing power, its bleaching power is weakened. Therefore, if the desilvering process is composed of a bath of a bleach-fixing solution, it is possible to achieve the desired purpose when processing a photosensitive material for printing with a small amount of developed silver. When processing a color photographic light-sensitive material, it has a drawback that the bleaching action is insufficient and desilvering is unsatisfactory.

Various bleaching accelerators have been investigated as a method for improving the disadvantages of the ferric ion complex salt of ferric aminopolycarboxylic acid. As such a bleaching accelerator,
Five-membered ring mercapto compounds as described, for example, in British Patent 1,138,842, Swiss Patent 336,2.
Although there are thiadiazole derivatives, thiourea derivatives, thiazole derivatives and the like as described in No. 57, they have not yet fully satisfied the recent demands for rapid processing in the art.

As another means for achieving rapid desilvering, there is a means for enhancing agitation in the desilvering process to speed up the supply of the bleaching agent and the fixing agent into the emulsion film of the light-sensitive material, resulting in increasing the desilvering rate. Proposed. For example, JP-A-62-18
No. 3460, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material, a method of improving the stirring effect by using a rotating means described in JP-A No. 62-183461, and a wiper provided in the solution. Examples include a method of moving the light-sensitive material while bringing the blade into contact with the emulsion surface to make the emulsion surface turbulent, thereby improving the stirring effect, and a method of increasing the circulation amount of the entire processing solution.

On the other hand, in Japanese Unexamined Patent Publication No. 1-206343, a method of colliding a jet stream of a treatment liquid with a strong oxidizing power 1,3
-A method for suppressing bleaching fog and improving desilvering property by combining with a diaminopropane tetraacetic acid ferric complex salt or the like is described.

The present inventor applied a liquid having such a bleaching ability for the purpose of rapid processing, and as a result, desired desilvering performance was obtained and bleaching fog was suppressed, but continuous processing was performed. It was found that the subsequent yellow stain and the magenta stain of the light-sensitive material deteriorated over time. Furthermore, it was also found that uneven processing occurs in continuous processing. It has been found that this tendency becomes remarkable when the replenishment of the color developing solution is low and the amount of eluate from the light-sensitive material and oxidative decomposition products in the color developing solution are increased. As described above, the conventionally known photosensitive materials and processing methods have various problems, and it is necessary to develop a further processing method.

[0009]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to carry out a continuous processing even in a processing in which the replenishing amount of a bleaching solution is reduced and the processing time (especially desilvering time) is shortened. It is an object of the present invention to provide a processing method for improving the yellow stain, the magenta stain after aging with wet heat, and the processing unevenness of the subsequent light-sensitive material.

[0010]

The above object was achieved by the following method. (1) A silver halide color photographic light-sensitive material in which at least one light-sensitive silver halide emulsion layer is provided on a support is imagewise exposed, then treated with a color developer, and then bleached. In the method of treating with a treatment solution having a bleaching ability, the treatment solution having a bleaching ability contains at least one metal chelate compound of a compound represented by the following general formula (I) and / or (II), and A method for processing a silver halide color photographic light-sensitive material, which comprises subjecting the emulsion surface of the light-sensitive material to a jet stream of a liquid having the bleaching power to make it process in a functional bath. General formula (I)

[0011]

Embedded image

(In the formula, Y ₁ represents a non-metal atom group necessary for forming an aromatic hydrocarbon ring or a heterocycle. R ₁ represents a substituent. N represents an integer of 0 to 4. .X R ₁ good .X ₁ be different may be the same when n represents an integer of 2 to 4 represents a hydrogen atom or -L ₁ -A _2
2 represents a hydrogen atom or -L ₄ -A _4. L ₁ , L ₃ and L ₄ each represent an alkylene group or an arylene group.
W ₁ represents a divalent linking group. A ₁ , A ₂ , A ₃ , A ₄ and A ₅ are carboxylic acid or its salt, sulfonic acid or its salt, phosphonic acid or its salt, hydroxy group, hydroxyalkyl group, carbamoyl group, acylamino group, sulfonamide group, respectively. Represents a sulfamoyl group, an alkoxy group, an alkylthio group or an amino group. ) General formula (II)

[0013]

[Chemical 4]

(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.
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 is a single bond, -O-, -S- or -N (Rw
) -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. ) In particular, the effect is (2) The method for processing a silver halide color photographic light-sensitive material as described in (1) above, wherein the color developer contains substantially no hydroxylamine. (3) After treatment with the treatment solution having the bleaching ability, the pH is 4.0 to
This is remarkable in the method of processing a silver halide photographic light-sensitive material described in (1) or (2) above, which is characterized in that the processing is carried out with a stabilizing processing solution in the range of 5.5.

The present invention will be described in detail below. In the present specification, the aliphatic group, aromatic hydrocarbon group and heterocyclic group are as follows unless otherwise specified. The aliphatic group means a substituted or unsubstituted, straight-chain, branched or cyclic alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted alkynyl group. The divalent aliphatic group is a divalent group of these aliphatic groups, and is a substituted or unsubstituted linear, branched or cyclic alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkynylene. Represents a group. As the aliphatic group, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a 2-hydroxypropyl group, a hexyl group,
Examples thereof include an octyl group, a vinyl group, a propenyl group, a butenyl group, a benzyl group and a phenethyl group.

The aromatic hydrocarbon group means a substituted or unsubstituted aryl group which may be monocyclic or may be condensed with an aromatic ring or a heterocycle. The divalent aromatic hydrocarbon group represents a substituted or unsubstituted arylene group which may be monocyclic or may be condensed with an aromatic ring or a heterocycle. Examples of the aromatic hydrocarbon group include a phenyl group, a 2-chlorophenyl group, a 3-methoxyphenyl group and a naphthyl group.

The heterocyclic group has at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom,
It represents a 3- to 10-membered, saturated or unsaturated, substituted or unsubstituted, monocyclic ring or a heterocyclic group which may be condensed with an aromatic ring or a heterocycle. As the heterocycle, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a thiadiazole ring, an oxadiazole ring, a quinoxaline ring,
Examples thereof include a tetrazole ring, a thiazole ring and an oxazole ring.

Further, each group in the present specification may be substituted unless otherwise specified, and examples of the substituent which they may have include an alkyl group, an aralkyl group, an alkenyl group and an alkynyl group. , Alkoxy group, aryl group, amino group, acylamino group, sulfonamide group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, acyl group, hydroxy group , Halogen atom, cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group, alkoxycarbonyl group, acyloxy group, nitro group, hydroxamic acid group, heterocyclic group and the like.

In the present invention, the treatment is carried out in the liquid having the bleaching ability while colliding the jet stream of the liquid having the bleaching ability with the emulsion surface. The jet of the liquid having the bleaching ability can be generated by sucking the liquid having the bleaching ability with a pump and discharging the liquid toward the emulsion surface. More specifically, it is pumped from a slit or nozzle provided facing the emulsion surface described in the section of the lower right column on page 3 to the lower right column on page 4 of JP-A-62-183460. A method of discharging the liquid that has been pressure-fed can be adopted.

A processing apparatus having a specific preferable stirring system will be described in detail. As a preferred automatic development processing apparatus, an automatic silver halide photographic light-sensitive material having a processing tank for processing the light-sensitive material and a conveying means for conveying the light-sensitive material through a predetermined path in the processing tank having the bleaching ability A conveyance processing device, wherein guides for supporting both ends of the photosensitive material are installed in the conveyance path of the photosensitive material in parallel with the conveyance direction,
On the emulsion surface of the light-sensitive material, the amount of the processing solution blown out per unit area of the jet outlet is 1 to 30 liters / cm ² , and between the jet outlet and the emulsion surface of the light-sensitive material. This is a photosensitive material processing apparatus provided with means for performing jet agitation under conditions where the distance is 10 mm or less.

More specifically, the stirring effect of the jet stream will be reduced as the distance between the jet outlet of the jet stream and the emulsion surface of the light-sensitive material increases, when the jet flow rate is constant. However, in the case of conveyance with a guide, compared with the case of conveyance without a guide using a normal leader, a sufficient stirring effect cannot be obtained with ordinary jet agitation,
It was found that rapid processing could not be accommodated. The distance between the jet outlet and the emulsion surface of the light-sensitive material must be 10 mm or less, and it is preferable that the jet outlet and the emulsion surface do not come into contact with each other. The distance between the outlet and the emulsion surface is 10 to 0.1 mm, preferably 5 to 0.5 mm,
More preferably, it is 3 to 0.8 mm.

At this time, the jet amount of the jet flow is determined by the automatic development.
To the extent that it does not hinder the transportation of photosensitive materials in the machine,
It is preferable to be as large as possible and 1 to 30 liters per minute
Torr / cm²Must be, preferably 1 minute
Between 2 and 25 liters / cm ²Is. These jets
The stirring conditions are, of course, the same as for ordinary desilvering processing.
However, especially when the desilvering processing time is set to 2 minutes or less,
The effect of the stirring on the photographic properties is clearly shown. This jet
Stirring is particularly performed by immersing the light-sensitive material in a liquid having a bleaching ability.
The initial stage of swelling by absorbing a liquid with bleaching ability, for example,
For example, 20% of the processing time in the processing tank after dipping the photosensitive material
Good photographic properties when the jet agitation is applied within the time
It was revealed that was obtained by rapid processing. Jet
Flow stirring is performed within 15% of the treatment time.
Preferably, it is performed within 10 to 1% of the time
More preferable.

As described above, it is particularly preferable in the desilvering process to provide jet agitation at the initial stage of dipping the photosensitive material in the processing bath in the processing bath. When jet agitation is performed, the liquid surface rises due to liquid agitation at the gas-liquid contact surface, and the processing liquid may overflow or air may be entrained due to vibration of the liquid surface. These are not preferable because they cause deterioration of the liquid due to mixing of the processing liquid into another adjacent processing layer or mixing of air into the processing liquid. Further, when the liquid level rises, the contact time between the photosensitive material and the processing liquid changes, which causes a problem that uniform processing cannot be performed. For this reason, it is preferable that the jetting direction of the jet agitation in the vicinity of the liquid surface is in the direction farther from the liquid surface (the direction toward the bottom of the processing tank) than the direction perpendicular to the photosensitive material conveying direction. The jet agitation outlets near the liquid surface refer to two outlets, the outlet closest to the portion where the photosensitive material is loaded into the processing liquid and the outlet closest to the portion where the photosensitive material is discharged from the processing bath. It is preferable that the blow-in direction is inclined in the same direction as the carrying direction in the part carried in, and the direction opposite to the carrying direction is tilted in the part carried out from the processing tank.

The preferred method and apparatus for processing a silver halide photographic light-sensitive material of the present invention exerts a remarkable effect when it is applied to rapid processing using a small processing apparatus.
Here, a small processing device is a desilvering processing condition of 2 minutes,
It refers to a processor having an ability to process 60 to 5 photosensitive materials of 35 mm × 24 sheets per hour, and preferably to a processor having a throughput of 50 to 10 per hour.

As a modified example of the means for performing jet agitation, there is a small jet agitation instrument in which a processing liquid supply pipe communicating with a processing liquid pressure pump is connected to a small box provided with a slit. A small number of small jet stirrers with only one slit installed at the desired mounting position in the treatment layer,
The jet stirring conditions can be easily adjusted by attaching the desired jetting direction.

When jet stirring is performed on a photosensitive material whose both ends are guided by guides, the photosensitive material may bend or be separated from the guide depending on the conditions of jet stirring. Therefore, it is preferable to provide the wall body on the surface facing the blowing direction of the jet agitation. The wall may be a flat guide or a freely rotatable roller which is arranged at a position where it can be blocked so that the photosensitive material is not separated from the guide by the blowing pressure of jet stirring. For the same purpose, it is also effective to prevent the bending of the photosensitive material by performing the second jet agitation from the direction opposite to the jetting direction of the jet agitation.

As the preferred silver halide photographic light-sensitive material processing apparatus of the present invention, it is preferable to apply the guide groove and jet stirring means to a tank having a bleaching ability, but it is also suitable to be applied to any processing tank in the processing apparatus. it can. From the viewpoint of processing efficiency, these are preferably used in the developing step, the desilvering step or the water washing (or stabilizing) step, and further, two or more kinds of these processing steps (processing tanks), especially the desilvering step and the water washing. It is preferably used for both baths in the (or stable) step.

The processing solution having a bleaching ability of the present invention will be described. First, the compound represented by formula (I) will be described in detail below. In the formula, Y ₁ represents a nonmetallic atom group necessary for forming an aromatic hydrocarbon ring or a heterocycle. The aromatic hydrocarbon group formed by Y ₁ is preferably an aromatic hydrocarbon group having 5 to 20 carbon atoms and may be a monocyclic ring or may be condensed with an aromatic ring or a heterocyclic ring. Rings are preferred. Examples of the aromatic hydrocarbon group formed by Y ₁ include a phenylene group and a naphthylene group. The heterocyclic group formed by Y ₁ is preferably a 5- to 6-membered monocyclic unsaturated heterocyclic group containing at least one nitrogen atom as a hetero atom. As the preferred heterocycle, those having a divalent carbon atom adjacent to each other in an imidazole ring, a pyrazole ring, a pyridine ring and the like are preferable. In the present invention, Y ₁ particularly preferably forms a phenylene group.

Examples of the substituent of R ₁ include an alkyl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, amino group, acylamino group, sulfonamide group, ureido group, urethane group and aryloxy group. , Sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, acyl group, hydroxy group, halogen atom, cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group, alkoxycarbonyl group, acyloxy Group, nitro group, hydroxamic acid group, heterocyclic group and the like. When it has a carbon atom, the substituent preferably has 1 to 10 total carbon atoms (hereinafter referred to as C number), and has 1 to 4 C atoms. R ₁ is preferably a halogen atom, an alkyl group having a C number of 1 to 4, and a C number of 1 to 4
Alkoxy group, C1-4 amino group, C2-4 acylamino group, C1-4 sulfonamide group, C0-4 sulfamoyl group, C1-4 alkylthio group, It is a hydroxy group, a sulfo group, a carboxy group or a phosphono group, and particularly preferably a halogen atom or an alkyl group having 1 to 4 C atoms, an alkoxy group having 1 to 4 C atoms or a carboxy group. As n, 0 or 1 is preferable, and 0 is particularly preferable.

In the present invention, X ₁ is -L ₁ -A.
₂ is preferred. As X ₂ , -L ₄ -A ₄ is preferable.
A _{1 to} A ₅ are each a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof,
It represents a hydroxyl group, a hydroxyalkyl group, a carbamoyl group, an acylamino group, a sulfonamide group, a sulfamoyl group, an alkoxy group, an alkylthio group or an amino group. Preferably, at least one of A _{1 to} A _{5 represents} a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, or a hydroxyl group.

Examples of the salts of carboxylic acid, sulfonic acid and phosphonic acid in A _{1 to} A ₅ include sodium salt, potassium salt, ammonium salt and calcium salt. The carbamoyl group, the acylamino group, the sulfonamide group, the sulfamoyl group, the alkoxy group, the alkylthio group and the amino group in A _{1 to} A ₅ may have a substituent, and as the substituent, those mentioned as R ₁ can be applied. . The carbamoyl group and sulfamoyl group in A _{1 to} A ₅ are preferably unsubstituted or substituted with an alkyl group, an aryl group or a heterocyclic group, and when having a substituent, a C number of 1 to 10, and more preferably The C number is 1 to 4. For example, as the carbamoyl group, carbamoyl,
Examples thereof include N-methylcarbamoyl, N, N-dimethylcarbamoyl and N- (4-sulfophenyl) carbamoyl. Examples of the sulfamoyl group include sulfamoyl and N-methylsulfamoyl. As the sulfonamide group for A _{1 to} A ₅ ,
An unsubstituted alkylsulfonamide group and an alkylsulfonamide group substituted with a substituent (preferably a carboxy group, a hydroxy group, a halogen atom) are preferable, more preferably a C number of 1 to 5, and further preferably a C number of 1. ~ 3. Examples of the alkylsulfonamide group include methanesulfonamide and trifluoromethanesulfonamide.

The acylamino group in A _{1 to} A ₅ is substituted with an unsubstituted alkylacylamino group or a substituent (preferably an alkyl group, an aryl group, a heterocyclic group, a halogen atom, a carboxy group or a hydroxy group). And an alkylacylamino group are more preferable, and a C number of 1 is more preferable.
An alkylacylamino group having 10 to 10 carbon atoms, an arylacylamino group having 6 to 10 C atoms, and a heterocyclic acylamino group having 1 to 10 C atoms, and more preferably an alkylacylamino group having 1 to 5 C atoms. Examples of the acylamino group include acetylamino, benzoylamino, t-butanamide, trifluoroacetylamino and the like. The alkoxy group and alkylthio group in A _{1 to} A ₅ are preferably those having a C number of 1 to 10, and more preferably those having a C number of 1 to 5, and examples thereof include methoxy, ethoxy, and methylthio. The amino group in A _{1 to} A ₅ is an unsubstituted amino group, an unsubstituted alkylamino group or an alkylamino group substituted with a substituent (preferably a carboxy group, a hydroxy group, a phosphono group or a sulfo group). Preferably, the C number is 1 to 10, more preferably the C number is 1 to 6.
belongs to. A ₁ is carboxylic acid or a salt thereof, or an alkylthio group or an alkoxy group substituted with a carboxylic acid or a salt thereof (ie, —Z ₁ -L ₅ —CO
OM (Z ₁ represents an oxygen atom or a sulfur atom, L ₅ represents an alkylene group, M represents a hydrogen atom or a cation), and a carboxylic acid or a salt thereof is most preferable. As A _{2 to} A ₅ , a carboxylic acid or a salt thereof, a phosphonic acid or a salt thereof, a sulfonic acid or a salt thereof, or a hydroxyalkyl group is more preferable, and a carboxylic acid or a salt thereof is most preferable.

The alkylene group for L ₁ , L ₃ and L ₄ may be linear, branched or cyclic and may be a substituent such as those mentioned for R ₁ (preferably a carboxylic acid or a salt thereof, a hydroxy group or a halogen atom). It may be substituted.
Preferably, it is one having a C number of 1 to 10, more preferably an alkylene group having a C number of 1 to 3, and further preferably-.
_{CH 2 -, - CH (CH} 3) -, - CH (C 2 H 5) -
Is. The arylene group for L ₁ , L ₃ and L ₄ may be monocyclic or may be condensed with an aromatic ring or a heterocyclic ring, and may have a substituent such as those described for R ₁ (preferably an alkyl group or an acylamino group). Group, alkylsulfonamide group, alkoxy group, sulfamoyl group, carbamoyl group, alkylthio group, sulfo group, phosphono group, acyl group, alkoxycarbonyl group, nitro group, carboxy group, hydroxy group, halogen atom, hydroxamic acid group) It may have been done. As L ₁ , L ₃ and L ₄ , an alkylene group is preferable. W ₁ is preferably a divalent linking group containing an alkylene group, an alkenylene group, an arylene group, a divalent heterocyclic group and / or a group consisting of a combination thereof. More preferably, it is represented by the general formula (W). General formula (W)

[0034]

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(In the formula, W ₂ , W ₃ and W ₅ each represent an alkylene group, and W ₄ represents

[0036]

[Chemical 6]

Represents Y ₁ ′, R ₁ ′ and n ′ have the same meanings as Y ₁ , R ₁ and n in formula (I). c represents an integer of 0 to 3, and d and e are 0 respectively.
Or represents 1. X ₁ is -O-, -S- or -N (R ₃ ).
Represents-. R ₃ represents a hydrogen atom, an alkyl group (eg, methyl, carboxymethyl, hydroxymethyl) or an aryl group (eg, phenyl, 4-sulfophenyl). ) As W ₁ , those in which c is 0 are preferable, and d and e
Is more preferably 0. The C number of W ₁ is preferably 1 to 20, more preferably 2 to 10, and most preferably 2 to 4. Examples of W ₁ include the following.

[0038]

[Chemical 7]

In the compound represented by the general formula (I) of the present invention, Y ₁ is an atomic group forming a phenylene group,
X ₁ is -L ₁ -A ₂ , X ₂ is -L ₄ -A ₄ , A _{1 to} A ₅ are carboxylic acids or salts thereof,
L ₁ , L ₃ and L ₄ are each an alkylene group having a C number of 1 to 3, W ₁ is an alkylene group having a C number of 2 to 4,
R ₁ is a halogen atom, an alkyl group having a C number of 1 to 4, an alkoxy group having a C number of 1 to 4, an amino group having a C number of 1 to 4, a C number of 2
To an acylamino group having 1 to 4 carbon atoms, a sulfonamide group having 1 to 4 carbon atoms, a sulfamoyl group having 0 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a hydroxy group, a sulfo group, a carboxy group or a phosphono group, and n is , 0 or 1 are particularly preferred. Specific examples of the compound represented by formula (I) are shown below.

[0040]

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[0041]

[Chemical 9]

[0042]

[Chemical 10]

[0043]

[Chemical 11]

The compound represented by the general formula (I) which serves as a ligand in the metal chelate compound of the compound represented by the general formula (I) of the present invention (may be simply referred to as the metal chelate compound of the present invention) is In addition to commercially available products, for example, "Journal of the Diamerican Society"
(Journal of the American Chemical Society), 80,80
It can be obtained by synthesizing with reference to 0 (1958) and the like.
For example, it can be synthesized by reacting an anthranilic acid derivative with a halogen-substituted carboxylic acid derivative, or by substituting a halogen atom of a halogen-substituted aromatic derivative with a diamine derivative and then reacting it with a halogen-substituted alkylcarboxylic acid. The compound represented by the general formula (I) is described in, for example, European Patent Publication No. 530828A1.

Next, the compound represented by the general formula (II) 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, it has 1 to 6 carbon atoms, and 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
4 is an alkylthio group, and examples thereof include methylthio, ethylthio and carboxymethylthio. ), 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 heterocycle, 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 1 to 2 atoms. It is a 5- to 6-membered aromatic heterocycle including.

Specific examples of the heterocycle include 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. The hetero ring is preferably 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 listed 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, 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 phenylene is more preferable. 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 meanings 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.

[0062]

[Chemical 12]

[0063]

[Chemical 13]

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. Further, 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 metal (eg Ca ²⁺ , Mg ²⁺ etc.), ammonium (eg ammonium, tetraethylammonium etc.), pyridinium, phosphonium (eg tetrabutylphosphonium,
Tetraphenylphosphonium etc.) and the like.
An inorganic cation is preferable, and an alkali metal ion is more preferable. Among the compounds represented by the general formula (II), preferably the following general formula (III) or (IV)
Is a compound represented by. General formula (III)

[0066]

Embedded image

(In the formula, R ^{1 ′} represents an aliphatic hydrocarbon group. The aliphatic hydrocarbon group represented by R ^{1 ′} has the general formula (I
It has the same meaning as the aliphatic hydrocarbon group represented by R ¹ in 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 (II), and the preferred ranges are also the same. ) General formula (IV)

[0068]

[Chemical 15]

(In the formula, R ^{1 ″} represents an aryl group. R
^The aryl group represented by ^{1 ″} is represented by R in the general formula (II).
It has the same meaning as the aryl group represented by ¹ , and the preferred range is also the same. L ¹ , L ² , 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 (II), 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)

[0071]

Embedded image

(In the formula, R ^{1 '} is R in the general formula (III).
It is synonymous with ^{1 '} and the preferred 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 (II), 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)

[0074]

[Chemical 17]

(In the formula, R ^{1 ″} is R in the general formula (IV).
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 (II), and their preferred ranges are also the same. )

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

[0077]

Embedded image

(In the formula, R ₁ ^' is R in the general formula (III).
It is synonymous with ^{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 (II), and the preferable range is also the same. L ³ , L ⁴ ,
M ¹ , M ² , M ³ and M ⁴ are each represented by the general formula (II)
Of the above, and the preferred range is also the same. ) Among the compounds represented by the general formula (VI), more preferred are the compounds represented by the following general formula (VIII). General formula (VIII)

[0079]

[Chemical 19]

(In the formula, R ^{1 ″} is R in the general formula (IV).
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 (II), and the preferable 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 (II), and the preferred ranges are also the same. )

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

[0082]

Embedded image

[0083]

[Chemical 21]

[0084]

[Chemical formula 22]

[0085]

[Chemical formula 23]

[0086]

[Chemical formula 24]

The above compounds may be used in the form of salts. The compound represented by the general formula (II) 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 structural characteristic of the general formula (II) is that a branched alkylene group is introduced between the carboxyl group of aminopolycarboxylic acid and N. Up to now, a branched alkylene chain between N and N'has been disclosed (Japanese Patent Laid-Open No. 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".

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) and so on. 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) and / or (II) with a metal salt. Examples of the metal salt reacted with the compound represented by the general formula (I) and / or (II) include, for example,
Examples thereof include ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, ferric oxide and the like.

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 a compound represented by the above general formula (I) and / or (II),
More preferably 25 to 100 mol%, most preferably 3
It is preferable to occupy 5 to 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 / or (II) and a metal salt, for example, a second sulfate. An iron salt, a ferric chloride 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) and / or (II) is used in a molar ratio of 1.0 or more with respect to the metal ion. This ratio is preferably large when the stability of the metal chelate compound is low, and is usually used 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 the fixing solution or an intermediate bath between the color developing step 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 so long as the effects of the present invention are not impaired (preferably, the molar ratio is 2/3 or less). As the bleaching agent which can be used in combination, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. As a typical bleaching agent, an organic complex salt of iron (III), for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, glycol etherdiaminetetraacetic acid, JP-A-4-121739,
Bleaching agents including iron 1,3-propylenediaminetetraacetic acid complex salts from the lower right column of the fourth page to the upper left column of the fifth page, carbamoyl bleaching agents described in JP-A-4-73647, European Patent Publication No. 52045, which includes a heterocyclic bleaching agent, N- (2-carboxyphenyl) iminodiacetic acid ferric complex salt described in Kaihei 4-174432.
No. 7, a bleaching agent described in EP-A-501479, a bleaching agent described in EP-A-567126, a bleaching agent described in JP-A-4-127145, and a JP-A-3-144446. Examples thereof include ferric aminopolycarboxylic acid salts or salts thereof described on page (11) of the publication, 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 containing an organic acid iron (III) complex salt, 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.

In the present invention, it is preferable that the color developing solution contains substantially no hydroxylamine. 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 preferable.

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-toluenesulfonates or sulphates. Two or more of these compounds can be used in combination depending on the purpose.

The amount of the aromatic primary amine developing agent used is
Preferably from 0.01 mol per liter of color developer.
0.2 mol, more preferably 0.02 mol to 0.1 mol. Within the preferable range of the amount of the aromatic primary amine developing agent used, the developing speed is improved and the rapid processing in which the development fog is suppressed becomes possible.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt,
It generally contains a development inhibitor such as bromide salt, iodide salt, benzimidazole, benzothiazole or mercapto compound, or an antifoggant. 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 catechol sulfonic acids, 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 reversal 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 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 way, in addition to providing a cover 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 is disclosed. The slit development processing method described in 63-216050 can be mentioned. In addition, a method of bringing a liquid such as liquid paraffin that covers the surface of the processing liquid or a low-oxidizing and / or non-oxidizing gas into contact with the surface of the processing liquid is also included. The reduction of the aperture ratio is preferably applied not only in both the color development and black and white development steps but also in the subsequent steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilizing. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

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 via 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 fatty acids substituted with ethylene oxide described in U.S. Pat. No. 4,839,262, U.S. Pat. No. 4,059,446 and Research Disclosure 191, 19104 (1980). It is preferable to contain the described polyoxyethylene compound and 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. Further, the replenishing amount of the adjusting bath is preferably 30 ml to 3000 ml per 1 m ² of the light-sensitive material, but particularly 50 ml to 150 ml.
It is preferably 0 ml. Treatment temperature of conditioning bath is 20 ℃
˜50 ° C. is preferable, but 30 ° C. to 40 ° C. is particularly preferable.

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 process is performed with a processing solution having a bleaching ability, and then a fixing process is performed 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 the 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 fixing ability means a processing solution containing a fixing agent among 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 3
It is particularly preferable when the replenishment amount is reduced to 0 to 450 ml. The processing temperature of the processing solution having a bleaching ability in the present invention is 20 to
The temperature is 55 ° C, preferably 30 to 50 ° C. The processing time is
From the viewpoint of quickness, the range of 10 seconds to 2 minutes is preferable, and the range of 20 seconds to 1 minute 30 seconds is particularly 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, as a rehalogenating agent for promoting the oxidation of silver. It is preferred to add a halide such as iodide. Further, an organic ligand that 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 bleaching ability of the present invention, the amount of the rehalogenating agent is appropriately 2 mol / liter or less, and in the case of the bleaching solution, it is preferably 0.01 to 2.0 mol / liter, and more preferably 0. 0.1 to 1.7 mol / liter, particularly preferably 0.1 to 0.6 mol / liter. In the bleach-fixing solution, 0.001-2.
0 mol / liter is preferable, 0.001 to 1.0 mol / liter is more preferable, and 0.001 to 0.5 mol / liter.
L is particularly preferred.

The processing solution having a bleaching ability or its pre-bath according to the present invention contains a bleaching accelerator, a corrosion inhibitor for preventing corrosion of the processing bath, a buffering agent for maintaining the pH of the solution, a fluorescent whitening agent, and a defoaming agent. Agents and the like are added as needed. For 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
No. 06,561 thiourea derivative, JP-A No. 58-16235, iodide, German Patent No. 2,748,430, polyethylene oxides, 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
A mercapto compound as described in Japanese Patent No. 42, JP-A-2-190856 is 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 carried out immediately after color development in a photographic light-sensitive material, the pH of the solution is controlled in order to suppress bleaching fog.
Is 7.0 or less, preferably 6.4 or less. Particularly in the case of a bleaching solution, 3.0 to 5.0 is preferable.
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 color print materials, a pH range of 3-7 is preferred. As the pH buffer for this purpose, any one can be used as long as it is difficult to be 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. A plurality of these buffers may be used in combination.

In order to adjust the pH of the processing solution having a bleaching ability to the above range, the above-mentioned acid and alkali agents (for example, aqueous ammonia, KOH, NaOH, potassium carbonate, sodium carbonate, imidazole, monoethanolamine, diethanolamine) are used. You may use together. Of these, 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 / liter.

With the recent increase in awareness of global environment conservation, 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 addition, in the present invention, the concentration of ammonium ion is 0.
1 mol / liter or less, preferably 0.0
8 mol / liter or less, more preferably 0.01 mol / liter
Less than or equal to 1 liter, particularly preferably not contained at all. In order to reduce the ammonium ion concentration to the range of the present invention, an alkali metal ion or an alkaline earth metal ion is preferable as an alternative cation species, an alkali metal ion is particularly preferable, and a lithium ion, a sodium ion, or a potassium ion is particularly preferable. However, specifically, sodium salts and potassium salts of an organic acid ferric iron complex as a bleaching agent, potassium bromide as a rehalogenating agent in a treatment liquid having a bleaching ability, sodium bromide, potassium nitrate, Examples thereof include sodium nitrate. Further, as the alkaline agent used for pH adjustment, potassium hydroxide,
Sodium hydroxide, potassium carbonate, sodium carbonate and the like are preferable.

The processing liquid having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance is kept extremely stable. Means known in the art can be used for the aeration, and blowing of air into the processing liquid having a bleaching ability or absorption of air using an ejector can be performed. At the time of blowing air, it is preferable to discharge the air into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Z-121, Eusing Process C-41, No. 3, issued by Eastman Kodak Company.
The matters described in the edition (1982), pages BL-1 to BL-2 can be used.

The processing solution having the bleaching ability of the present invention is
The overflow solution after use in the treatment can be recovered, the components can be added to modify the composition, and then the overflow solution can be reused. Such usage is usually called regeneration, but the present invention can also favor such regeneration. For details of the reproduction, see Fuji Film Processing Manual issued by Fuji Photo Film Co., Ltd., Fuji Color Negative Film, CN-16 processing (revised August 1990), pp. 39-.
The matters described on page 40 can be applied. 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 added directly without using excess water.

Regarding the regeneration of the processing solution having the bleaching ability,
In addition to the aeration mentioned above, "Basics of photographic engineering-silver salt photography-" (edited by the Photographic Society of Japan, published by Corona Publishing Co., 1979)
Year)) etc. can be used. Specifically, in addition to electrolytic regeneration, there is a method of regenerating bleaching solution with bromic acid, zincic acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using catalyst, bromic acid, ozone, etc. Can be mentioned.
In electrolytic regeneration, the cathode and the anode are put in the same bleaching bath, or the anode bath and the cathode bath are regenerated by using a diaphragm to separate the baths. The fixing solution can be reprocessed at the same time. The fixing solution and the bleach-fixing solution are regenerated by electrolytically reducing accumulated silver ions. Other,
It is also preferable to remove accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance.

The concentration of the fixing agent in the processing solution having fixing ability is 0.2 to 3.0 mol, preferably 0.5 to 2.0 mol, and more preferably 1.1 to 1 mol, per liter of the bleach-fixing solution or the fixing solution. It is 1.8 mol. In this preferable range of the concentration of the fixing agent, the desilvering rate is improved, and stain generation after processing is effectively prevented.

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. Regarding these, 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
It is described in 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, etc. Can be mentioned. Of these, thiosulfates and mesoions are preferable. 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. Further, by using two or more fixing agents in combination, more rapid fixing can be performed. For example, in addition to ammonium thiosulfate or sodium thiosulfate, it is also preferable to use the above-mentioned ammonium thiocyanate, imidazole, thiourea, thioether, etc. in this case. It is preferably added in the range of 01 to 100 mol%.

The pH of the fixing solution depends on the kind of the fixing agent, but is generally 3.0 to 9.0, and particularly when thiosulfate is used, 5.8 to 8.0 is a stable fixing. It is preferable for obtaining performance.

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.

The bleach-fixing solution and the fixing solution containing the metal chelate compound of the present invention preferably contain 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 liquid 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. Further, the replenishing amount of the processing solution having fixing ability in the present invention is 1 per 1 m ² of the light-sensitive material.
It is set to 0 to 1000 ml, preferably 20 to 80
It is 0 ml, and it is particularly preferable that the supplement 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.
° C. 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 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,
Examples thereof include N-allylmorpholine and N-benzoylpiperazine.

The total time of 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 stain generation after the 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 the desilvering rate. 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.

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, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions It can be set in a wide range. 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 (19
May 55 issue), you can ask for it. According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively as a solution to such a problem. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" (1986)
Sankyo Publishing, Sanitary Technology Association, "Sterilization, sterilization, and fungicide technology for microorganisms" (1982) Industrial Technology Association, Fungicide described in "Encyclopedia of fungicides and fungicides" (ed. 1986) Can also be used.

Rinsing water in processing 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.

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.

In order to adjust the pH of the stabilizing solution to the above range, the above-mentioned acid and alkaline agents (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 for stabilizing the dye image, for example, benzaldehydes such as formalin and 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 addition amount of these compounds is preferably 0.001 to 0.02 mol per liter of the stabilizing solution, but the lower the free formaldehyde concentration in the stabilizing solution is, the less the formaldehyde gas is scattered, which is preferable. 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 13753 are preferred. Particularly, azoles such as 1,2,4-triazole described in JP-A-4-359249 (corresponding to European Patent Publication No. 519190A2) and 1,4-bis (1,2,4)
The combined use of azolylmethylamine and its derivatives such as -triazol-1-ylmethyl) piperazine is preferable because of high image stability and low formaldehyde vapor pressure. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, US Pat.
It is also preferable to contain an alkanolamine described in JP-A-86,583 or a preservative that can be contained in the fixing solution or the bleach-fixing solution, for example, a sulfinic acid compound described in JP-A-1-231510. .

The washing water and the stabilizing solution may contain various surfactants in order to prevent unevenness of water droplets when the photosensitive material after processing is dried. 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. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

Various chelating agents are preferably contained in 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 and diethylenetriamine-N, N,
Examples thereof include organic phosphonic acids such as N ', N'-tetramethylenephosphonic acid, and hydrolyzates of maleic anhydride polymers described in European Patent 345,172A1.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are 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 replenishing solution. The specific method for replenishing water is not particularly limited, but among them, a monitor water tank different from the bleaching tank described in JP-A-1-254959 and 1-254960 is installed, and water in the monitor water tank is installed. The amount of water vaporized in the bleaching tank is calculated from the amount of water vaporized in the bleaching tank, and the bleaching tank is replenished with water in proportion to the amount of water vaporized.
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.
As the water for correcting the evaporation of each treatment liquid, tap water may be used, but deionized water or sterilized water which is preferably used in the above washing step is preferably used.

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 remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. 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 treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. 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 concentrated or concentrated liquid preparation, a granule, a powder, a tablet, a paste or an emulsion. As an example of such a treating agent, JP-A-63-1
7453 is a liquid agent stored in a container with low oxygen permeability,
19655 and 4-230748 are vacuum packed powders or granules, and 4-21951 are granules containing a water-soluble polymer,
JP-A-51-61837 and JP-A-6-102628 have tablets and special tables
00485 discloses a paste-like treatment agent, and any of them can be preferably used, but from the viewpoint of ease 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 level of oxygen permeability required. For a liquid such as a color developing solution which is easily oxidized, a material having low oxygen permeability is preferable, and specifically, polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials have a thickness of 500 to 1500 μm, are used for a container, 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 treating the color negative film and the color paper with the same treatment liquid, the cost of the treatment machine can be reduced and the treatment can be simplified.

The light-sensitive material of the present invention may have at least one light-sensitive layer provided on a support. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. Is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by sequentially exposing two layers, a high-speed emulsion layer and a low-speed emulsion layer, to a support as described in DE 1,121,470 or GB 923,045. It is preferable to arrange them so that the degree is low. In addition, JP-A-57-112751, 62-200350, 62-2
As described in 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity 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 photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH It can be installed in the order of. Further, as described in JP-B-55-34932, from the side farthest from the support, the blue-sensitive layer / GH / RH / GL
It can also be arranged in the order of / RL. In addition, JP-A-56-2573
8 and 62-63936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest 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 a silver halide emulsion layer having a higher sensitivity than the middle layer. An example is an arrangement in which low silver halide emulsion layers are arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of such three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / high-sensitivity layer is separated from the side distant from the support. You may arrange in order of a speed emulsion layer / a low speed emulsion layer. 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 case of 4 layers or more,
The arrangement may be changed as described above. In order to improve color reproducibility, BL, GL, described in US 4,663,271, 4,705,744, 4,707,436, JP-A-62-160448, and 63-89850.
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as RL, adjacent to or close to the main photosensitive layer.

The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, which contains about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about 0.2 μm or less
It may be large-sized grains up to 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-23.
Page, "I. Emulsion preparation and type
s) ”and ibid. No. 18716 (November 1979), p. 648, ibid.
o.307105 (November 1989), pages 863-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Gl).
afkides, Chemie et Phisique Photographique, Paul M
ontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion C
hemistry, Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VL Ze
likman, et al., Making and Coating Photographic Em
ulsion, Focal Press, 1964) and the like.

US 3,574,628, US 3,655,394 and GB 1,4
The monodisperse emulsions described in 13,748 are also preferred. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutof, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226, US 4,414,310,
It can be easily prepared by the method described in 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, and may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion is a surface latent image type that forms a latent image mainly on the surface,
Either an internal latent image type formed inside the grain or a type having a latent image both on the surface and inside may be used, but it is necessary that the emulsion is a negative type. Of the internal latent image types, JP-A-6
The core / shell type internal latent image type emulsion described in 3-264740 may be used, and its preparation method is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are RD No.17643 and RD No.187.
16 and No. 307105, and the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. US Pat. No. 4,082,553, the surface of which is covered with silver halide grains, US Pat. No. 4,626,498, and JP-A-59-21.
4852, a silver halide grain in which the inside of the grain is fogged,
It is preferred to apply colloidal silver to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is described in US 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 inside may have a different halogen composition.
As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm,
It is particularly preferably 0.05 to 0.6 μm. The grain shape may be regular grains or polydisperse emulsions, but monodisperse grains (weight of silver halide grains or grain number of at least 95
% Having a particle size within ± 40% of the average particle size).

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 bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide, if necessary. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grain does not need to be optically sensitized nor spectrally sensitized. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be contained in the fine silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the table 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, 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, 26-27 Pages 650 Right column 875-876 Pages Surfactants 9. Static 27 pages 650 Page right columns 876-877 Inhibitors 10. Matting agents 878-879

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 (bottom right of page 12), L-77 (bottom right of page 13); EP 456,257, A-4 -6
3 (134 pages), A-4 -73, -75 (139 pages); EP 486,965 M-4, -6
(Page 26), M-7 (page 27); M-45 of EP 571,959A (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: JP-A-2-44345, P-1, P-5 (page 11).

Examples of couplers in which the coloring 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. The coupler for correcting the unwanted absorption of the color forming dye is a yellow-colored cyan coupler 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
Page), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), US 4,837,136 (2) (column 8),
The colorless masking couplers represented by formula (A) in claim 1 of WO92 / 11575 (in particular, the exemplified compounds on pages 36 to 45) are preferred. Examples of the compound (including a coupler) which reacts with an oxidized product of a developing agent to release a photographically useful compound residue include the following. Development inhibitor releasing compound: EP 37
Compounds represented by formulas (I), (II), (III) and (IV) described on page 11 of 8,236A1 (particularly T-101 (page 30), T-104 (page 31), T-113 ( 36
Page), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP436, 93
Compounds represented by formula (I) on page 7 of 8A2 (especially D-4
9 (page 51)), compounds represented by formula (1) of EP 568,037A (particularly (23) (page 11)), formulas (I), (II), and EP 440,195A2 on pages 5 to 6, Compounds represented by (III) (especially I- on page 29)
(1)); Bleach accelerator releasing compounds: compounds represented by formulas (I) and (I ′) on page 5 of EP 310,125A2 (particularly (60) and (6 on page 61)
1)) and a compound represented by the 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
Compounds represented by formulas (1), (2), and (3) in 4,656,123, column 3 (particularly (I-22) in column 25) and EP 450,637A2
ExZK-2, lines 75-36, page 75; Compounds that release dye groups only upon elimination: Formula (I) of claim 1 of US 4,857,447
Compounds represented by (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 of 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, column 2, lines 5-10 (especially compound 1 (column 3); stain inhibitor: EP 298321A, 4).
Formulas (I)-(III) on pages 30-33, especially I-47, 72, III-1, 27 (24
~ Page 48); 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
Pp.), US 5,122,444, columns 25-38, II-1 to III-23, especially
III-10, EP 471347A, pages 8-12, I-1 to III-4, especially II-
2, US 5,139,931 columns 32-40 A-1 to 48, especially A-39,
42; Materials that reduce the use of color-enhancing agents or color-mixing inhibitors: 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), JP-A-2-
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; Stabilizers, antifoggants: 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
Compounds 1-22 represented by formula (I) of 8,622 (columns 3-1
0), a compound (1) represented by the formula (I) of US 4,923,788 ~
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
(Page 9), compounds (3) to (6 represented by formula (I) of EP 520938A.
6) (pages 10 to 44) and the compound HBT-1 represented by the formula (III).
~ 10 (page 14), compounds represented by formula (1) of 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 include
For example, the RD. Page 28 of NO.17643, 6 of the same 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. 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 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 is the saturated film thickness. 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 swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive 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 add an ultraviolet absorber, an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, and a surface active agent. The swelling ratio of this back layer is 150-500
% Is preferred. 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. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. 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 RD. No.176
43, pp. 28-29, ibid. No. 18716, 651 left column-right column, and ibid.
Development can be carried out by a usual method described in No. 307105, pages 880 to 881.

When the light-sensitive material of the present invention is used as a color negative film, the support may be any one of 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 surface-treated with silica and / or alumina or an organic material. Further, the magnetic particles may be surface-treated with a silane coupling agent or a titanium coupling agent, as described in JP-A-6-101632.
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 Coalescence (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The above resin has a Tg of -40 to 300 ° C and a weight average molecular weight of 20,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose tripropionate, and other cellulose derivatives, acrylic resins, polyvinyl acetal resins, and gelatin is also preferable. Cellulose di (tri) acetate is particularly preferable. The binder can be hardened by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based cross-linking agent include isocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates and polyalcohols (for example, tolylene diisocyanate). 3 mol of isocyanate and 1 m of trimethylolpropane
ol reaction product), and polyisocyanates produced 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, etc. are preferable and a combination thereof is also preferable, as in the method described in JP-A-6-35092. The dispersant 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 of the magnetic particles and the binder is preferably 0.5: 100 to 60: 100.
And more preferably 1: 100 to 30: 100. The coating amount of magnetic particles is 0.005 to 3 g / m ² , preferably 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 the form of a stripe. 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 roll, gravure, kiss, cast, spray, dip, bar, extrusion and the like can be used, and the coating liquid described in JP-A-5-341436 is preferable.

In the magnetic recording layer, improvement of lubricity, curl adjustment,
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. The surface of these abrasives may be 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 preferably the same binder as that of the magnetic recording layer is used. US Pat. No. 5,336,589, US Pat. No. 5,250,404, US Pat.
5,229,259, 5,215,874 and EP 466,130.

As a material for the support, Japanese Patent Laid-Open No. 4-124 is used.
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. Polyethylene naphthalate described in Functional Materials, February 1991, pp. 20-28 is preferable.

Next, the polyester support preferably used in the present invention will be described. For details including the light-sensitive material, processing, cartridges and examples described later, open technical report, official technique No. 94-6023 (Invention Society; 1994.3.15.). The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components. As the aromatic dicarboxylic acid, 2,6-, 1,5-, 1,4-, and 2,7-naphthalenedicarboxylic acid, terephthalic acid are used. 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. Among them, polyethylene 2 is particularly preferable.
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 subjected to a heat treatment at a heat treatment temperature of 40 ° C. or higher and lower than Tg, 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 the heat treatment may be performed while cooling. The heat treatment time is 0.1 hour or more and 1500 hours or less, and more preferably 0.5 hour or more and 200 hours or less. The heat treatment of the support may be carried out in the form of a roll or may be carried out while being conveyed in the form of a web.
Irregularity may be imparted to the surface (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ may be applied) to improve the surface state. Further, it is desirable to devise a technique such as giving a knurl to the end and slightly raising only the end to prevent the cut end of the winding core from being exposed. These heat treatments are after the support film formation, the surface treatment,
It may be carried out at any stage after coating the back layer (antistatic agent, slip agent, etc.) and after coating the undercoat layer. Preferred is after the antistatic agent is applied. An ultraviolet absorber may be kneaded into this polyester. Also, to prevent light piping,
The purpose can be achieved by kneading a commercially available dye or pigment for polyester such as Diaresin manufactured by Mitsubishi Kasei or 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 and ozone oxidation treatment can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment and glow treatment are preferable. Next, the undercoating method may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid,
Starting with copolymers starting from monomers selected from acrylic acid, itaconic acid, maleic anhydride and the like, polyethyleneimine, epoxy resins, grafted gelatin, nitrocellulose and gelatin are listed. 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,
At least one selected from MoO ₃ and V ₂ O ₅ has a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less, and a particle size of 0.001 to 1.0 μm crystalline metal. Fine particles of oxides or their complex oxides (Sb, P, B, In, S, Si, C, etc.), and further sol-like metal oxides or fine particles of these complex oxides. The content in the sensitive material is 5 to
500 mg / m ² are preferred and particularly preferably 10 to 350 mg / m ^2. The ratio of the conductive crystalline oxide or its composite oxide to the binder is preferably 1/300 to 100/1, more preferably 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. The preferred sliding property is a dynamic friction coefficient of 0.
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 photosensitive material surface is replaced as the mating material, the values are almost the same. Examples of slip agents that can be used in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, and esters of higher fatty acids and higher alcohols. Polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, and polydiethylsiloxane. Styrylmethyl siloxane, polymethylphenyl siloxane, etc. can be used. The addition layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane and ester having a long chain alkyl group are preferable.

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be either on the emulsion side or the back side, but it is particularly preferable to add it to the outermost layer on the emulsion side.
The matting agent may be soluble in the treatment liquid or insoluble in the treatment liquid, 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 add fine particles of 0.8 μm or less at the same time in order to enhance the matting property. For example, polymethylmethacrylate (0.2 μm), poly (methylmethacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)), polystyrene Particles (0.25 μm), colloidal silica (0.03 μm)
Is mentioned.

The packaging body (patrone) for accommodating the light-sensitive material of the present invention may be any of the existing ones or known ones, and in particular, US Pat. No. 4,834,306, FIGS.
In the shape described in g.3 and in US Pat. No. 4,846,418.
The ones shown in FIGS. 1 to 3 or US Pat. No. 5,29
Those described in Figs. 1 to 7 of No. 6,887 are preferable. The film formats used in the present invention include the 135 type specified in Japanese Industrial Standard "JIS.K-7519 (1982)", Japanese Patent Laid-Open No. 4-123047, 4-123059, 4-123051, 4-12
In addition to the formats described in Nos. 5560, 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 cartridge of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are described in JP-A 1-312537 and 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured by using a plastic in which carbon black, a pigment and the like are kneaded in order to impart a light shielding property. 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 case of the cartridge is 30 cm ³ or less, preferably 25 cm ³ or less. The weight of the plastic used in the cartridge and cartridge case is preferably 5 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, the structure may be such that the leading end of the film is housed in the cartridge body and the leading end of the film is fed to the outside from the port portion of the cartridge by rotating the spool shaft in the feeding direction of the film. 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. Further, the raw film and the developed photographic film may be housed in the same new cartridge, or may be 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. For incorporation, it is preferable to use various precursors of color developing agents. For example U.S. Pat.
42,597 Indoaniline compounds, 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 contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. 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.

[0170]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

Example 1 On a subbed cellulose triacetate film support,
Each layer having the following composition was coated in multiple layers to form a photosensitive layer, and a sample 101 which was a multilayer color photosensitive material was prepared.

(Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye The numeral corresponding to each component indicates the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver. However, for the sensitizing dye, the coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer.

First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.60 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) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide 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 Iodobromide 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 iodobromide 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 iodobromide Emulsion E 0.15 Silver iodobromide Emulsion F Silver 0.10 Silver iodobromide 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 Iodobromide 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 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide 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 1.33

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 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide 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 1.8

Fourteenth layer (second protective layer) Silver iodobromide 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 the storability, processability, pressure resistance, antifungal / bacteriostatic property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0188]

[Table 1]

In Table 1, (1) Emulsions J to L were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Emulsions A to I were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. ing. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the example of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains using a high voltage electron microscope. (5) Emulsion L is a double-structured grain containing an internal high iodine core described in JP-A-60-143331.

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 p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) of the aqueous solution 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 material was dispersed for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the 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.

In the same manner, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively.
ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of EP549,489A. The average particle size was 0.06 μm.

[0192]

[Chemical 25]

[0193]

[Chemical formula 26]

[0194]

[Chemical 27]

[0195]

[Chemical 28]

[0196]

[Chemical 29]

[0197]

Embedded image

[0198]

[Chemical 31]

[0199]

Embedded image

[0200]

[Chemical 33]

[0201]

Embedded image

[0202]

Embedded image

[0203]

Embedded image

[0204]

Embedded image

[0205]

[Chemical 38]

[0206]

[Chemical Formula 39]

[0207]

[Chemical 40]

The sample 101 described above was tested for color temperature of 4800K.
Was subjected to continuous gradation wedge exposure, and a running process (until the cumulative replenishment amount of the color developing solution became three times the tank capacity) was performed by a cine type automatic developing machine with the following processing steps and processing solutions. In addition, as shown in Table 2, the bleaching solution was changed in the bleaching agent used, and the bleaching solution was exchanged in sequence for each running treatment. Further, the stirring in the bleaching tank is performed by a jet stirring method (hereinafter sometimes simply referred to as J) applied to the bleaching tank of Example 1 of JP-A-1-206343 and a circulation stirring method (hereinafter simply referred to as N). (Sometimes said). The former is a system that constitutes the present invention, and the latter is a comparative example. The jet stirring conditions for the treatment in the bleaching solution are:
The blowing rate was 3 liters / cm ² per minute, and the distance to the emulsion surface was 3 mm. 10 jet outlets for jet agitation were provided, and the first jet agitation was performed 2 seconds after the immersion in the treatment liquid (at the time of 5.0% of the bleaching treatment step).

The processing steps and processing liquid compositions are shown below.

(Processing step) Processing time Processing temperature Replenishment amount * Tank capacity Color development 1 minute 00 seconds 45.0 ° C 260 ml 2.5 liter Bleach 30 seconds 45.0 ° C 130 ml 2 liter Fixed (1) 30 seconds 40.0 ° C -2 Liter set (2) 30 seconds 40.0 ℃ 400 ml 2 liter water wash 15 s 40.0 ℃ 800 ml 2 liter stability (1) 15 s 40.0 ℃ −2 liter stability (2) 15 s 40.0 ℃ 130 ml 2 liter dry Drying 40 seconds 65 ° C * Replenishment amount per 1 m ² of the light-sensitive material is a countercurrent system of the fixing solution and the stabilizing solution from (2) to (1), and the overflow solution of washing water was 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 of the light-sensitive material.
^{It was} 40 ml, 33 ml, 38 ml, and 65 ml per ² respectively. The crossover time is 3 seconds in all cases, and this time is included in the processing time of the previous step. As evaporation correction in each tank, JP-A-3-280
As described in No. 042, 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 processing 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 sulfite 4.0 6.7 Potassium carbonate 40.0 40.0 Potassium bromide 2.0-Iodide Potassium 1.3 mg-Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 13.2 17.2 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.0 14.5 Add water 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) Metal chelating agent 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 Maleic 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

(Rinsing 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.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

(Stabilizer) Common to tank liquid and replenisher (unit: g) Succinic acid 0.6 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 (Prepared with ammonia water and nitric acid) 5.0

After the running process was completed, the sample 101 was exposed to a continuous tone wedge exposure at a color temperature of 4800K, and each of the 6 types of bleaching solution and the stirring method was combined to carry out the process as shown in Table 2. The change with time of yellow stain and magenta stain due to running and the processing unevenness were evaluated.

Yellow-Stain: The density of the sample treated by the above method before and after running was measured, and the unexposed area (Dmin) measured with blue light (B light) was read from the characteristic curve. And as below, yellow-dye Dmi
The change in n by running was calculated. Change in Dmin due to running (ΔDmin (B)) = (Dmin after running)-(Dmin before running) Stain temporal change: From the characteristic curve, the density was measured for the photosensitive material processed by the above method after running. Each Dmin measured with green light (G light) was read. Then, store the sample after measurement under the following conditions, and
n was measured similarly. Then, the change with time of the stain of the magenta dye was determined as follows. Storage conditions: 70 ° C, relative humidity 70%, 2 weeks Change in stain over time (ΔDmin (G)) = (Dmin (G) after storage)-(DDmin (G) before storage) -Processing unevenness: with camera 1000 samples 101 taken
The frames were visually observed to evaluate the occurrence frequency of unevenness. still,
When two irregularities were generated in one frame, it was treated as if there were two irregularities. Occurrence frequency of unevenness = (number of unevenness / 1000) × 100 (%)

The results obtained by the above method are shown in Table 2.

[0220]

[Table 2]

From the results of Table 2, according to the embodiment of the present invention,
It has been found that yellow stain in continuous processing, magenta stain over time in moist heat, and even processing unevenness can be suppressed. Although it is known that rapid desilvering and suppression of bleaching fog can be achieved by jet-type stirring which is an aspect of the present invention, in combination with the bleaching agent of the present invention, image preservation in continuous processing is achieved. It was an unexpected effect that brought about the effect of deterring sexual deterioration.

In Experiment No. 12 of Example 1, the time of the first jet agitation in the bleaching solution was 3 seconds (7.5% of the bleaching process step) and 5 seconds (12. 5
%), After 8 seconds (20.0%), the same evaluation was performed, and it was confirmed that it was more effective to perform jet stirring at the initial stage of the bleaching treatment.

Example 2 On a subbed cellulose triacetate film support,
1 from the 20th line on the left column on page 96 of Kogi No. 94-6023
The photosensitive layer described on page 14 was applied to prepare Sample 201, which is a multilayer color photosensitive material. Sample 2 described above
01 is subjected to continuous gradation wedge exposure at a color temperature of 4800K, and running processing is performed by a cine type automatic developing machine with the following processing steps and processing solutions (until the cumulative replenishment amount of the color developing solution reaches three times the tank capacity). )Did. For the color developing solution and the bleach-fixing solution, as shown in Table 3, the preservatives used and the bleaching agents used were changed, and the respective preservatives and the bleaching agents were sequentially exchanged for running processing. Further, the stirring in the bleach-fixing tank is performed by the jet stirring method (hereinafter sometimes simply referred to as J) and the circulation stirring method (hereinafter simply referred to as N) applied to the bleaching tank described in Example 1 of the present application. There are two). The jet stirring conditions in the bleach-fixing tank were 5 l / cm ² per minute and a distance of 2 mm. Jet outlets for jet agitation were provided at 15 places, and the first jet agitation was performed 2 seconds after the immersion in the processing liquid (at the time of 3.3% of the bleach-fix processing step).

After the running treatment was completed, various combined treatments as shown in Table 3 were performed on the sample 201, and the same evaluation as in Example 1 was performed. The results are shown in Table 3.

[0225]

[Table 3]

According to the embodiment of the present invention, it has been found that good results can be obtained even if the processing steps are changed. Also, experiment N
Both o.4 and No.8 are embodiments of the present invention, but it was a surprising effect that the photographic property in continuous processing was further improved by not using hydroxylamine in the color developing solution.

In Experiment No. 11 of Example 2, the blowing distance in the bleach-fix solution was 3 mm, 5 mm, 1
When the distance was changed to 0 mm and the same evaluation was performed, it was confirmed that the shorter the distance between the air outlet and the emulsion surface, the more effective.

Details of the processing executed are shown below.

(Processing step) Processing time Processing temperature Replenishment amount * Tank capacity Color development 1 minute 00 seconds 45.0 ° C 260 ml 2.5 liter Bleach fixing 1 minute 00 seconds 40.0 ° C 600 ml 2.5 liter Water wash 20 seconds 40.0 ° C 800 ml 1.5 Stabilization (1) 20 seconds 40.0 ℃ -1.5 liters Stability (2) 20 seconds 40.0 ℃ 400 milliliters 1.5 liters Dry 50 seconds 65 ℃ * Replenishment amount per 1 m ² of light-sensitive material Stabilizer is from (2) (1 ) To the bleach-fixing bath. still,
The amount of developing solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the washing process and the amount of washing solution brought into the stabilizing process were 40 ml / m ² of the light-sensitive material and 38, respectively.
They were milliliters, 45 milliliters, and 65 milliliters. The crossover time is 3 seconds in all cases, 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 processing 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 sulfite 4.0 6.7 Potassium carbonate 40.0 40.0 Potassium bromide 2.0-Potassium iodide 1.3 mg -Preservatives listed in Table 3 0.45 mol 0.60 mol 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulphate 11.0 14.5 Water was added to 1.0 liter 1.0 liter pH (hydroxylation Adjust with potassium and sulfuric acid) 10.05 10.30

(Bleach-fixing solution) Tank solution (g) Replenisher solution (g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 40.0 96.0 Ferric complex salt shown in Table 3 0.10 mol 0.24 mol Ethylenediaminetetraacetic acid 6.0 14.4 Succinic acid 12.0 28.8 Ammonium sulfite 20 80 Ammonium thiosulfate aqueous solution (700 g / l) 290 700 Ammonium methanesulfinate 5.0 20 Ammonium iodide 2.0 1.7 Add water 1.0 liter 1.0 liter pH (prepared with ammonia water and nitric acid) 6.0 5.8

(Washing Water) The same composition as the washing water of Example 1 of the present application.

(Stabilizing Solution) Common to tank solution and replenishing solution The same composition as the stabilizing solution of Example 1 of the present application.

Example 3 Sample 101 described in Example 1 of the present application was subjected to continuous tone wedge exposure at a color temperature of 4800K, and a running process (cumulative of developing solution) was carried out by a cine type automatic developing machine with the following processing steps and processing solutions. Until the replenishment amount is three times the tank capacity). The stabilizing solution was changed as shown in Table 4, and each of them was sequentially replaced and a running process was performed. The stirring in the bleach-fixing tank was carried out by the jet stirring method (hereinafter sometimes simply referred to as J) applied to the bleach-fixing tank described in Example 2 of the present application. Sample 10 after running
1 continuous color wedge exposure at a color temperature of 4800K,
As shown in Table 4, the treatment was performed in combination with four types of stabilizing solution compositions, and the same evaluation as in Example 1 was performed. The results are shown in Table 4.

[0235]

[Table 4]

Although all the examples of the present invention are aspects of the present invention, by adjusting the pH of the stabilizing solution to the range of 4 to 5.5, the replenishment after the desilvering step can be lowered and the continuous treatment can be performed. It was found that the effect of suppressing deterioration of image storability in the example becomes large.

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. As the silver recovery device, a small electrolytic silver recovery device was used, in which the anode was carbon and the cathode was stainless steel, and the current density was 0.5 A / dm ² . Specifically, the one shown in FIG. 1 of JP-A-6-175305 was used. However, no regenerant was used. That is, 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 returned to the original bleach-fixing tank 20 through the filter 24 by the pump 23. Overflow from silver recovery device 22 25
Is collected in the regeneration tank 26 per 1 liter of overflow, blown with air for about 2 hours when the amount of collection reaches 1 liter, and then sent to the replenishing tank 30 of the bleach-fixer by the pump 29. Remaining liquid (100
ml) was discharged as a waste liquid.

For the stabilization treatment, a 5-stage multi-chamber stabilizing tank was arranged horizontally and used, and a countercurrent cascade was carried out. Specifically, the one shown in FIG. 1 of JP-A-5-66540 was used.
A schematic diagram of the processor is shown in FIG. 2 of JP-A-6-175305.
Is shown in. However, the overflow solution of the first stabilizing solution is discharged as a waste solution without being cascaded to the bleach-fixing tank of the previous bath, and the reverse osmosis membrane (R
O) No equipment was installed.

The processing steps are shown below.

[Process] (Process) (Processing time) (Processing temperature) (Replenishment amount) ^{* 1} (Tank capacity / liter) Color development 1 minute 00 seconds 45 ℃ 260ml 2.5 Bleach fixing 1 minute 00 seconds 40 ℃ 260ml 2.5 Stable (1) 15 seconds 40 ℃ -0.8 stable (2) 15 seconds 40 ℃ -0.8 stable (3) 15 seconds 40 ℃ -0.8 stable (4) 15 seconds 40 ℃ -0.8 stable (5) 15 seconds 40 ℃ 260ml 0.8 dry燥50 sec 70 ℃ - - * 1 replenishment rate amount per photographic material 1 m ²

The composition of the processing liquid is shown below.

(Color developer) The same composition as the color developer of Example 1 of the present application.

(Bleach-fixing solution) Tank solution (g) Replenishing solution (g) Ferric complex salt of II-22 0.16 mol 0.184 mol Ethylenediaminetetraacetic acid 6.0 6.9 Succinic acid 12.0 13.8 Ammonium sulfite 20 40 Ammonium thiosulfate aqueous solution (700 g / l) ) 300 345 Ammonium methanesulfinate 5.0 15 Ammonium iodide 2.0-Add water 1.0 liter 1.0 liter pH (prepared with ammonia water and nitric acid) 6.0 5.8

(Stabilizer A) Mother liquor and replenisher common tap water is prepared by using H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type strongly basic anion exchange resin (Amberlite IRA). -4
00) packed in a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg of sodium dichloroisocyanate /
Liter, 150 mg / liter of sodium sulfate, and 200 mg / liter of polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) were added. The pH of this liquid was in the range of 6.5-7.5.

(Stable solution B) 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-Benzisothiazolin-3-one 0.05 Chlorinated sodium isocyanurate 0.02 Add water 1.0 liter pH (adjusted with nitric acid and aqueous ammonia) 6.0

(Stable solution C) common to mother solution and replenisher solution Same composition as stable solution B pH (adjusted with nitric acid and ammonia water) 5.5

(Stabilizer D) common to mother liquor and replenisher Same composition as stabilizer B pH (adjusted with nitric acid and ammonia water) 5.0

Example 4 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 100
After drying 3 parts by weight and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy Co., Ltd.) as an ultraviolet absorber, 300 ° C.
After melting at T, it is extruded from a T-die, longitudinally stretched 3.3 times at 140 ° C, then transversely stretched 3.3 times at 130 ° C, and heat-set at 250 ° C for 6 seconds to form a PEN with a thickness of 90μm.
I got a film. This PEN film contains blue dye, magenta dye, and yellow dye (I-1, I-4, I-6, I-24, I-26, I- in Public Technical Report No. 94-6023). 27, II-5)
Was added in an appropriate amount. Furthermore, it was wound on a stainless steel core having a diameter of 20 cm and subjected to a heat history of 110 ° C. for 48 hours to obtain a support with less curling tendency.

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 thereof, and then gelatin 0.1 g / m ² and sodium α-sulfodiene on each side. -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 , a polyamide-epichlorohydrin polycondensate 0.02 g / m ² undercoat liquid was applied (10 cc / m ² , using a bar coater), and an undercoat layer was provided on the high temperature surface side during stretching. Dry 1
The test was carried out at 15 ° C for 6 minutes (the temperature of the rollers and the conveying device in the drying zone are 115 ° C). 3) Coating of back layer After the undercoating, an antistatic layer having the following composition, a magnetic recording layer and a sliding layer were coated as back layers on one surface of the support.

3-1) Coating of antistatic layer A tin oxide-antimony oxide composite having an average particle size of 0.005 μm has a specific resistance of 5 Ω · cm and is a dispersion of fine particle powder (secondary agglomerated particle size of about 0.08 μm). 0.2 g / m ^2, gelatin 0.05g / m ^2, (C
H ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02g / m ² , poly (degree of polymerization 1
0) Oxyethylene-p-nonylphenol 0.005g / m ²
And Resorcin. 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, uniaxial 0.03μm, saturation magnetization 89emu / g, Fe ^{+ 2} / Fe ⁺³ = 6/94, surface is treated with aluminum oxide silicon oxide at 2% by weight of iron oxide) 0.06g / m ² is diacetyl cellulose 1.2 g / m ² (iron oxide was dispersed in an open kneader and a sand mill), C ₂ H ₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) ₃ as a curing agent
0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent,
A magnetic recording layer having a thickness of 1.2 μm was obtained. As a matting agent, silica particles (0.3 μm) and abrasive aluminum oxide (0.15 μm) coated with 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) were coated, respectively.
It was added at 10 mg / m ² . Drying was carried out at 115 ° C for 6 minutes (all rollers and conveyors in the drying zone are 115
° C). The color density increase of D ^B of the magnetic recording layer by the X-light (blue filter) is about 0.1, the saturation magnetization moment of the magnetic recording layer is 4.2 emu / g, the coercive force is 7.3 × 10 ⁴ A / m, and the squareness ratio is 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
The (compound b, 9 mg / m ² ) mixture was applied. This mixture is xylene / propylene monomethyl ether (1/1)
It was melted at 105 ° C. in water, poured into and dispersed in propylene monomethyl ether (10 times amount) at room temperature to prepare a dispersion (average particle diameter 0.01 μm) in acetone, and then added. Silica particles (0.3 μm) as a matting agent and 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (aluminum oxide coated with 15% by weight (0.15 μm) as an abrasive were 15 mg / m ² and The amount of drying was 115
C., 6 minutes (115 ° C. for all rollers and conveyors in the drying zone). The sliding layer had an excellent dynamic friction coefficient of 0.06 (stainless steel ball of 5 mmφ, load 100 g, speed of 6 cm / min), static friction coefficient of 0.07 (clip method), and the dynamic friction coefficient of the emulsion surface, which will be described later, was 0.12. .

4) Coating of Photosensitive Layer Next, the photosensitive layer described in Sample 101 described in Example 1 of the present application was coated to form a multilayer color photosensitive material, Sample 40.
Created 1.

The light-sensitive material prepared as described above is applied in a 24 mm width,
Cut it to 160 cm, and add a 2 mm square perforation 0.7 mm from the width of one side of the photosensitive material.
Two are provided at 5.8 mm intervals. We have made a set of these two sets at intervals of 32 mm, and are shown in FIGS. 1 to 7 of US 5,296,887.
It was placed in the plastic film cartridge described in. An FM signal was recorded on this sample at a feed rate of 1,000 / s during the above-mentioned perforation of the photosensitive material by using a head gap of 2,000 turns and a head gap of 5 μm from the coated surface side of the magnetic recording layer. After recording the FM signal, the emulsion surface was uniformly exposed for 1,000 cms, and each processing was performed by the methods described below, and then the emulsion was stored again in the original plastic film cartridge.

The sample 401 described above was subjected to the same treatment and the same evaluation as those in Example 3 of the present application. The sample 401 that had been exposed and processed was stored again in the original plastic film cartridge. Similar to the results of Example 3 of the present application, good results were obtained in the present invention even in the light-sensitive material having a magnetic recording layer on the back surface opposite to the emulsion layer.

Example 5 Using the same photosensitive material processing apparatus as in Example 4 of the present application, in order to prevent the vibration of the sample 401, a free roller as a wall or an opposing surface was provided on the surface facing the jet stirring jet outlet. The effect of performing the second jet stirring from the surface to be examined was examined. The jet agitation distance was 2 mm, and the blowing amount was 5 liters / cm ² and 30 liters / cm per minute, respectively.
^The state of separation from the guide in each case was observed and evaluated by changing to ² , 20 liters / cm ² , and 10 liters / cm ² . Better results were obtained in the present invention by increasing the jet amount of the jet flow. However, when the jet amount was stronger than the preferable jet agitation condition, when there was no wall on the facing surface, Detachment of the material occurs, but when the preferable conditions of the jet agitation of the present invention are satisfied, the light-sensitive material is bent, but the detachment does not occur. However, it was confirmed that the stability of the light-sensitive material was improved when there was a wall body or a jet-jet agitation blowing on the opposing surface.

[0257]

According to the constitution of the present invention, it is possible to prevent deterioration of photographic properties in continuous processing even in low replenishment and rapid processing.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G03C 11/00 501 G03C 11/00 501

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material in which at least one light-sensitive silver halide emulsion layer is provided on a support, is imagewise exposed and then treated with a color developing solution, and then is bleached. In the method of treating with a treatment liquid having the formula (1), the treatment liquid having the bleaching ability is represented by the following general formula (I) and / or (II)
At least one of the metal chelate compounds of the compound represented by
A method of processing a silver halide color photographic light-sensitive material, which comprises subjecting the emulsion surface of the light-sensitive material to a jet of a liquid having the bleaching power in a bath containing a seed and having the bleaching power. . General formula (I) (In the formula, Y ₁ represents a non-metal atom group necessary for forming an aromatic hydrocarbon ring or a heterocycle. R ₁ represents a substituent.
n represents an integer of 0 to 4. When n represents an integer of 2 to 4, R ₁ may be the same or different. X
₁ represents a hydrogen atom or -L ₁ -A ₂ . X ₂ represents a hydrogen atom or -L ₄ -A _4. L ₁ , L ₃ and L ₄ each represent an alkylene group or an arylene group. W ₁ represents a divalent linking group. A ₁ , A ₂ , A ₃ , A ₄ and A ₅ are each a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, a hydroxy group, a hydroxyalkyl group, a carbamoyl group, an acylamino group,
Sulfonamide group, sulfamoyl group, alkoxy group,
It represents an alkylthio group or an amino group. ) General formula (II): (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,
It 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)-. Rw 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 method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the color developer contains substantially no hydroxylamine. 3. The pH after treatment with the treatment liquid having the bleaching ability
3. The method for processing a silver halide photographic light-sensitive material according to claim 1 or 2, wherein the processing is carried out with a stabilizing processing solution having a ratio of 4.0 to 5.5.