JPH07306504A - Photographic processing composition and processing method - Google Patents

Abstract

PURPOSE:To obtain the stable processing composition not causing precipitation and sludge, even if metal ions mix into it, and reduction of an effective component in a processing solution and not producing a component exerting a photographically unfavorable effect by incorporating a specified compound. CONSTITUTION:The photosensitive material image-exposed is processed with a processing solution containing at least one kind of the compound represented by the formula in which X is a cyclic aliphatic group; each of X1 and X2 is H, -L1-A2, or a cyclic aliphatic group; L is a divalent aliphatic group; L1 is alkylene; each of A1 and A2 is -COOM, -OH, -SO3M, or -PO(OM)2; M is H or a cation; and W is a divalent bonding group having a divalent aliphatic group and/or arylene.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a processing composition and processing method for silver halide photographic light-sensitive materials, and more particularly to a photographic processing containing a novel chelating agent for masking metal ions harmful to photographic processing. Compositions and treatment methods.

[0002]

2. Description of the Related Art Generally, a silver halide black-and-white photographic light-sensitive material is exposed and then processed by processing steps such as black-and-white development, fixing and washing, to obtain a silver halide color light-sensitive material (hereinafter referred to as a color light-sensitive material). Is subjected to processing steps such as color development, desilvering, washing with water and stabilization after exposure. The silver halide color reversal light-sensitive material is subjected to processing steps such as black and white development after exposure, color development, desilvering, washing with water and stabilization after reversal processing.

In the color developing step in the processing of color light-sensitive materials, the exposed silver halide grains are reduced by the color developing agent to silver, and the produced color developing agent oxidant reacts with the coupler to form an image dye. To form.
In the subsequent desilvering step, the developed silver generated in the developing step is oxidized to a silver salt by a bleaching agent having an oxidizing action (bleaching), and further, with a fixing agent which forms soluble silver, it is exposed to light with the unused silver halide. Removed from layer (fixed). For details of these processing steps and their composition, see James, "The Theory of Photograph" by James (4th edition).
ic Process "4'thedition) (1977), Research Disclosure No. 17643, pp. 28-29, No. 1
8716, 651 left column to right column, same No. 307105, 8
80 to 881 pages.

In addition to the above basic processing steps, various auxiliary steps are added for the purpose of maintaining the photographic and physical qualities of the dye image or maintaining the stability of processing. For example, washing step, stabilization step, hardening step,
Stopping process etc. are included.

The above-mentioned processing steps are generally carried out by an automatic developing machine. From a large-scale developing station equipped with a large automatic developing machine, a small automatic developing machine called a minilab has recently been installed in a store. Photo processing has been carried out in various places up to a photo shop, and along with this, there have been cases where the processing performance deteriorates.

One of the major causes is the mixing of metal ions into the treatment liquid. Different metal ions enter the processing liquid through different routes. For example, calcium, magnesium, and iron ions in some cases, and calcium contained in gelatin of the light-sensitive material are mixed into the processing solution through the water used for preparing the processing solution.
In addition, the iron chelate used in the processing solution having a bleaching ability spatters into the developer solution in the pre-bath, and the solution impregnated in the film is brought in, so that the ions contained in the pre-bath are removed. It may be brought in.

The influence of the mixed ions differs depending on the ions and the treatment liquid. Calcium and magnesium ions mixed in the developer react with carbonate, which is generally used as a buffering agent, to cause precipitation and sludge, which causes problems such as clogging of the circulation filter of the automatic processor and stains on the film processing. . When a transition metal salt such as iron ion is mixed in the developer, a para-phenylenediamine color developing agent, a hydroquinone, a black developing agent such as monol, or
Further, the decomposition of preservatives such as hydroxylamines and sulfites causes remarkable deterioration of photographic properties.

Further, when a transition metal such as iron ion is mixed in a bleaching solution containing hydrogen peroxide or persulfate, the stability of the solution is remarkably lowered and a problem such as poor bleaching occurs. Also in the fixing solution, in the case of a fixing solution using a normal thiosulfate as a fixing agent, the stability is lowered due to the incorporation of a transition metal salt, resulting in turbidity or sludge in the solution. As a result, clogging of the filter of the automatic processor reduces the circulating flow rate, resulting in poor stability and processing stains on the film. This phenomenon in the fixer also occurs in the wash water that follows the fixer. Especially, when the amount of wash water is reduced, the liquid exchange rate in the tank decreases, and the decomposition of thiosulfate called sulfuration and the precipitation of silver sulfide occur. Generation problems are extremely likely to occur. When such a state is exhibited, fatal stains often occur on the film surface.

In a stable solution prepared by using hard water containing a large amount of calcium and magnesium, bacteria are generated by using these as a nutrient source to cause turbidity in the solution and film stain. In addition, when transition metal-based ions such as iron ions are mixed, they remain in the film, which deteriorates the storability of the processed film. As described above, since the mixing of metal ions into the treatment liquid causes various adverse effects, an effective ionic masking agent has been strongly desired.

As a method for solving the above-mentioned problems, a chelating agent which masks metal ions has been used. For example,
Aminopolycarboxylic acids (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid) described in JP-B Nos. 48-30496 and 44-30232, or JP-A-56-97347, JP-B-56-39359 and West German Patent No. 2 227,639, or organic phosphonic acids described in JP-A Nos. 52-102726 and 53-42.
No. 730, No. 54-12127, No. 55-1262.
41, 55-65954, etc., and phosphonocarboxylic acids described in JP-A-58-195845, 5
Examples thereof include compounds described in 8-203440 and JP-B-53-40900.

[0011]

Although some of these compounds have been put to practical use, their performance has not been fully satisfactory. For example, ethylenediaminetetraacetic acid has a large hiding power for calcium ions, but when it is added to a developer, it accelerates the decomposition of the developing agent and the preservative of the developing agent in the presence of iron ions, resulting in a decrease in image density and an increase in fog. This causes deterioration of photographic quality. Further, for example, alkylidene diphosphonic acid does not cause such a bad effect even in the presence of iron ions, but a treatment liquid prepared with hard water containing a large amount of calcium generates a solid substance (tar), which causes There is a problem such as a failure. A chelating agent described in JP-A-5-66527 can be mentioned as a compound capable of simultaneously solving the problems found in both of these compounds and the above-mentioned problems. However, it has been difficult to maintain sufficient performance of these compounds under more severe use conditions such as an increase in processing temperature and an extension of the residence time of the processing liquid.

In particular, in recent years, the replenishment amount of the photographic processing liquid has been decreasing more and more due to the increasing social demand for environmental protection, and the retention time of the processing liquid in the processing machine becomes longer accordingly. . Further, due to the demand for speeding up, there is a tendency that the concentration of the developing agent, the bleaching agent, and the fixing agent is increased, and the temperature of the processing liquid is increased. Therefore, in particular, there has been a demand for the development of a novel chelating agent which is capable of effectively concealing metal ions accumulated even in a highly concentrated treatment solution for a long period of time without causing harmful effects.

Accordingly, it is a first object of the present invention to provide a photographic processing composition which does not generate precipitation or sludge even when metal ions are mixed therein. The second object is to provide a stable processing composition which does not reduce the active ingredient in the processing solution and does not produce the ingredient which adversely affects the photograph even when the metal ions are mixed. A third object is to provide a processing composition and a processing method using the same, in which the deterioration of the image storability caused by the residual metal ions in the processing composition remaining in the processed photosensitive material is improved. . A fourth object is to provide a treatment composition and a treatment method using the treatment composition, which can sufficiently maintain the performance even under more severe use conditions by increasing the treatment temperature and extending the residence time of the treatment liquid. is there.

[0014]

The above object was achieved by the following method. That is, a processing composition for a silver halide photographic light-sensitive material containing a compound represented by the following general formula (I) and a processing method using the same. General formula (I)

[0015]

[Chemical 3]

(In the formula, X represents a cycloaliphatic group. X ₁ and X ₂ each represent a hydrogen atom, -L ₁ -A ₂ or a cycloaliphatic group. L represents a divalent aliphatic group. L ₁ represents an alkylene group, A ₁ and A ₂ are each —COOM,
-OH, it represents a -SO ₃ M or -PO (OM) _2. M represents a hydrogen atom or a cation. W represents a divalent linking group containing a divalent aliphatic group and / or an arylene group. )

First, the compound represented by formula (I) will be described in detail below. Among the compounds represented by the general formula (I), preferably the following general formula (II) or (III)
Is a compound represented by. More preferably, the general formula (I
Among the compounds represented by the general formula (II), the compound represented by the general formula (II) is more preferable, and the compound represented by the following general formula (IV) is more preferable. Most preferably, it is a compound represented by the following general formula (V). General formula (II)

[0018]

[Chemical 4]

(X, X ₁ , L, A ₁ and W are represented by the general formula (I)
Are synonymous with each. L ₁ ′ and A ₂ ′ have the same meanings as L ₁ and A ₂ in formula (I), respectively. ) General formula (III)

[0020]

[Chemical 5]

(X, W, L, L ₁ , A ₁ and A ₂ have the same meanings as in formula (I). X ₂ 'represents a cycloaliphatic group.) Formula (IV)

[0022]

[Chemical 6]

(X, W, L, L ₁ , A ₁ and A ₂ have the same meanings as in formula (I). L ₁ 'and A ₂ '
Are respectively synonymous with L ₁ and A ₂ in the general formula (I). ) General formula (V)

[0024]

[Chemical 7]

(W, L, L ₁ , A ₁ and A ₂ have the same meanings as in formula (I). L ₁ 'and A ₂ '
Are respectively synonymous with L ₁ and A ₂ in the general formula (I). A ₃ has the same meaning as A _{1 in} formula (I). Z represents a carbon atom group necessary for forming a cycloaliphatic group. A ₃
The bond between the carbon atom substituted with and the carbon atom substituted with the nitrogen atom may be a single bond or a double bond. R represents a substituent, and n represents an integer of 0 to 8. )

Among the compounds represented by the general formula (V), the compound having the most excellent performance is the compound represented by the following general formula (VI). General formula (VI)

[0027]

[Chemical 8]

[0028] (W, the L and L ₁ are as defined respectively in formula (I) .L ₁ 'has the same meaning as L ₁ in the general formula (I) .Z form a cyclic aliphatic group R represents a substituent, n represents an integer of 0 to 8. M _a , M _b , M _c and M _d have the same meanings as M in formula (I). )

X represents a cycloaliphatic group. The cyclic aliphatic group may be monocyclic or bicyclic. Further, the cyclic aliphatic group is
It may be a saturated aliphatic group or an unsaturated aliphatic group. However, aromatic groups are not included. The number of carbon atoms forming the cycloaliphatic group is 3 to 20, preferably 5 or 6. Especially preferably, it is 6. Examples of the cycloaliphatic group include cyclohexyl, cyclopentyl, cyclohexenyl, cyclohexadienyl and the like. When the cycloaliphatic group has an unsaturated bond, the number of unsaturated bonds is 1
It is preferably -5, more preferably 1-2. Also,
The position of the unsaturated bond may be anywhere in the cyclic aliphatic group, but is preferably a position containing a carbon atom bonded to the amino group of the general formula (I) (for example, 1-cyclohexenyl group, 1 , 3-cyclohexadienyl group). The cyclic aliphatic group represented by X is preferably a monocyclic ring, and more preferably a saturated monocyclic ring. Most preferred is the cyclohexyl group.

This cyclic aliphatic group may have a substituent, and the substituent is an alkyl group (eg, methyl, ethyl, iso-propyl, preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms). ), An aralkyl group (eg, phenylmethyl, preferably 6 to 20 carbon atoms, more preferably 6 carbon atoms).
-10), an alkenyl group (eg allyl, preferably 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms), an alkoxy group (eg methoxy, ethoxy, preferably 1 to 1 carbon atoms).
0, more preferably 1 to 5), an aryl group (eg phenyl, p-methylphenyl, preferably 6 to 2 carbon atoms).
0, more preferably 6 to 10), an acylamino group (eg acetylamino group, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), a sulfonylamino group (eg methanesulfonylamino, preferably 1 to 10 carbon atoms). , More preferably 1 to 5), a ureido group (for example, methylureido, preferably 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms).
5), an alkoxycarbonylamino group (for example, methoxycarbonylamino, preferably 1 to 10 carbon atoms, more preferably 1 to 5), an aryloxycarbonylamino group (for example, phenyloxycarbonylamino, preferably 6 to 20 carbon atoms) Preferably 6-10), an aryloxy group (eg phenyloxy, preferably 6 carbon atoms)
˜20, more preferably 6 to 10), a sulfamoyl group (eg, methylsulfamoyl, preferably 0 to 10 carbon atoms).
10, more preferably 0 to 5), a carbamoyl group (eg, carbamoyl, methylcarbamoyl, preferably 1 to 10 carbon atoms, more preferably 1 to 5), a mercapto group,
Alkylthio group (eg, methylthio, carboxymethylthio, preferably 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms)
5), an arylthio group (eg phenylthio, preferably 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms), a sulfonyl group (eg methanesulfonyl, preferably 1 carbon atoms).
-10, more preferably 1 to 5), a sulfinyl group (for example, methanesulfinyl, preferably 1 to 10 carbon atoms,
More preferably 1 to 5), a hydroxy group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom), a cyano group, a sulfo group, a carboxyl group, a phosphono group, an amino group (for example, methylamino, preferably a carbon number of 0 to 0). 10, more preferably 0 to 5), an aryloxycarbonyl group (eg phenyloxycarbonyl, preferably 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms), an acyl group (eg acetyl, benzoyl, preferably 1 carbon atoms). 20,
More preferably 1 to 10), an alkoxycarbonyl group (for example, methoxycarbonyl, preferably 2 to 1 carbon atoms).
2, more preferably 2 to 6), an acyloxy group (eg acetoxy, preferably 2 to 12 carbon atoms, more preferably 2 to 6), a nitro group, a hydroxamic acid group, a heterocyclic group (eg pyridyl, furyl, thienyl). And the like, and these substituents may be further substituted. Preferred as the substituent of the cyclic aliphatic group are an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, a sulfo group, a carboxyl group, a phosphono group, an acyl group, an amino group, an alkyl group, an alkoxy group, a halogen atom,
A hydroxy group, a sulfo group and a carboxyl group are particularly preferable.

X ₁ and X ₂ are each a hydrogen atom, -L ₁
-A _2, represents a cyclic aliphatic group. The cycloaliphatic group represented by X ₁ and X ₂ has the same meaning as the cycloaliphatic group represented by X. X ₁ and X ₂ are preferably a hydrogen atom or-
L ₁ -A ₂ . Particularly preferably, it is -L ₁ -A ₂ .

X ₂ 'represents a cycloaliphatic group. The cycloaliphatic group represented by X ₂ 'has the same meaning as the cycloaliphatic group represented by X.

L represents a divalent aliphatic group. As the divalent aliphatic group, a linear, branched or cyclic alkylene group (for example, a methylene group, an ethylene group, a cyclohexylene group, a cyclopentylene group, preferably 1 to 10 carbon atoms,
More preferably 1 to 6), alkenylene group (eg vinylene group, propenylene group, cyclohexenylene group, preferably 2 to 10 carbon atoms, more preferably 2 to 6), alkynylene group (eg ethynylene group, preferably carbon number). Two
-10, more preferably 2-6). These divalent aliphatic groups may have a substituent, for example, X
The thing which was mentioned as a substituent which the cyclic aliphatic group represented by can be applied, and a preferable thing as a substituent is an alkyl group, an alkoxy group, a hydroxy group, an aryl group, a sulfo group, a carboxyl group, Is a phosphono group,
An alkyl group, an alkoxy group, a hydroxy group and a carboxyl group are particularly preferable. Moreover, these substituents may be further substituted. The divalent aliphatic group is preferably an alkylene group, more preferably a linear alkylene group. The linear alkylene group is particularly preferably a methylene group or an ethylene group.

L ₁ and L ₁ 'represent an alkylene group. Examples of the alkylene group include a linear, branched, or cyclic alkylene group (eg, methylene group, ethylene group, cyclohexylene group, cyclopentylene group). The number of carbon atoms forming the alkylene group is preferably 1-10, more preferably 1-6. Further, this alkylene group may have a substituent, and for example, those exemplified as the substituents which the cycloaliphatic group represented by X may have are applicable. Preferable substituents are an alkyl group, an alkoxy group, a hydroxy group, an aryl group, a sulfo group, a carboxyl group and a phosphono group, and an alkyl group, an alkoxy group, a hydroxy group and a carboxyl group are particularly preferable. Moreover, these substituents may be further substituted. The alkylene group is preferably a linear alkylene group, and particularly preferably a methylene group or an ethylene group.

A ₁ , A ₂ , A ₂ 'and A ₃ are --COO
M, represents -OH, -SO ₃ M, or -PO (OM) _2, M represents a hydrogen atom, or a cation. A ₁ , A ₂ ,
Of the groups represented by A ₂ 'and A ₃ , preferably -CO
OM and -OH, more preferably -COOM. The cation represented by M may be an organic cation or an inorganic cation. Further, when there are two or more cations in one molecule, they may be different cations. Examples of the cation include ammonium (eg ammonium, tetraethylammonium), alkali metal (eg lithium, sodium, potassium), alkaline earth metal (eg calcium, magnesium, barium) and pyridinium. An inorganic cation is preferable, and an alkali metal is more preferable.

R represents a substituent. As the substituent, for example, those mentioned as the substituent which the cyclic aliphatic group represented by X may have can be applied. Preferred as the substituent are an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, a sulfo group, a carboxyl group, a phosphono group,
An acyl group and an amino group, and an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a sulfo group, and a carboxyl group are particularly preferable. Moreover, these substituents may be further substituted.

N represents an integer of 0-8. n is preferably 0 to 4, and particularly preferably 0 or 1. Z represents a carbon atom group necessary for forming a cycloaliphatic group. The cyclic aliphatic group may be monocyclic or bicyclic.
It is preferably a monocyclic ring, and examples thereof include a cyclohexyl group, a cyclopentyl group, a cyclohexenyl group, and a cyclohexadienyl group. The cycloaliphatic group may be saturated or unsaturated. However, aromatic groups are not included. The cyclic aliphatic group is preferably an aliphatic group containing no unsaturated bond. The number of carbon atoms forming the cycloaliphatic group is 3 to 1
0 is preferable, and 5 or 6 is more preferable. Especially preferably, it is 6. The most preferred cycloaliphatic group is the cyclohexyl group. The bond between the carbon substituted with A ₃ and the carbon substituted with nitrogen may be a single bond or a double bond. It is preferably a single bond.

The divalent linking group represented by W is preferably represented by the following general formula (W). Formula _{(W) - (W 1 -D} ) q - (W 2) r - (D'-W 3) s - ( wherein, W _1, W ₂ and W ₃ are different even in the same Also, it represents a divalent aliphatic group, an arylene group, an aralkylene group or a single bond, and D and D ′ are each −
It represents O-, -S-, -N ( _Rw )-, -C (O)-or a divalent nitrogen-containing heterocyclic group. R _w is a hydrogen atom, —COOM ₂ , —PO ₃ M ₃ M ₄ , —OH or —S.
It represents an alkyl group or an aryl group which may be substituted with O ₃ M ₅ . M ₂ , M ₃ , M ₄ and M ₅ each have the same meaning as M in formula (I). q and s represent the integer of 0-3. When q is 2 or 3, W ₁ -D may be the same or different. Similarly, when s is 2 or 3, D′-W ₃ may be the same or different.
r represents an integer of 0 or 1. However, q, r, and s do not become 0 at the same time, and at that time, q that is not 0,
W ₁ , W ₂ and W ₃ in r and s are not single bonds. )

W ₁ , W ₂ and W ₃ may be the same or different, and may be a linear or branched divalent aliphatic group having 1 to 8 carbon atoms or a cyclic group having 5 to 10 carbon atoms. Divalent aliphatic group, C6-10 arylene group, C7-1
0 represents an aralkylene group or a single bond. W ₁ , W ₂ and W ₃ are preferably linear or branched divalent aliphatic groups or single bonds. More preferably, it is a linear or branched alkylene group. R _w is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be substituted with —COOM ₂ , —PO ₃ M ₃ M ₄ , —OH or —SO ₃ M ^5. Represents a group. The divalent nitrogen-containing heterocyclic group for D and D ′ is preferably a 5- or 6-membered ring in which the hetero atom is nitrogen (eg, imidazolyl, pyridyl, pyrrolyl), and is adjacent to the ring such as an imidazolyl group. and W ₁ at carbon atom
And those bound to W ₂ are more preferred. These W
The linking group represented by may have a substituent, and as the substituent, those exemplified as the substituents which the cyclic aliphatic group represented by X may have are applicable. W ₁ , W
_{As 2} and W ₃ , an alkylene group is preferable, and an alkylene group having 2 to 4 carbon atoms is more preferable.

Q and s represent an integer of 0 to 3. When q is 2 or 3, W ₁ -D may be the same or different. Similarly, when s is 2 or 3, D′-W ₃ may be the same or different. q and s are 0-2
Is preferred, 0 or 1 is more preferred, and 0 is particularly preferred. r represents an integer of 0 or 1. r is preferably 1. q, r, and s never become 0 at the same time, and in that case, W ₁ , W ₂ , W in q, r, and s that are not 0
₃ is never a single bond. )

A preferred combination of q, r and s is
(Q = 0, r = 1, s = 0), (q = 1, r = 1, s =
0), (q = 0, r = 1, s = 1), (q = 1, r =
1, s = 1), (q = 1, r = 0, s = 1), (q =
2, r = 1, s = 0), and more preferably (q =
0, r = 1, s = 0), (q = 1, r = 1, s = 0),
(Q = 0, r = 1, s = 1). The most preferred combination is (q = 0, r = 1, s = 0). Most preferably, the divalent linking group represented by W is ethylene,
They are trimethylene, tetramethylene and 1,2-propylene. Specific examples of W include the following.

[0042]

[Chemical 9]

[0043]

[Chemical 10]

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

[0045]

[Chemical 11]

[0046]

[Chemical 12]

[0047]

[Chemical 13]

[0048]

[Chemical 14]

[0049]

[Chemical 15]

[0050]

[Chemical 16]

The compound represented by the general formula (I) of the present invention is described in "Journal of the American Chemical Society", Vol. 78, pages 2723 to 2727 (1956).
(Journal of the American Chemical Society vol78.
2723-2727 (1956)) and the method of synthesizing the N-substituted ethylenediaminetriacetic acid and the method according to it. Representative examples of the compound represented by formula (I) of the present invention are shown below.

[0052]

[Chemical 17]

That is, an alicyclic ketone derivative is reacted with an excess amount of a diamine derivative, and hydrogen reduction is performed to obtain an intermediate (A).
Can be obtained (method 1). Another synthetic method is a method of substituting a halogen atom of a halogen-substituted alicyclic derivative with a diamine derivative (method 2). After separating these intermediates (A) and (B), the intermediate can be further reacted with a halogen-substituted alkylcarboxylic acid or the like to obtain the desired product.

Synthesis of compound 6

[0055]

[Chemical 18]

The starting material, trans-2-bromocyclohexanecarboxylic acid, is described in "Journal of the American Chemical Society", Vol. 77, pages 1594 to 1598 (1955) (Journal of the American Chemical Societies).
ty vol77.1594-1598 (1955)) for reference. The obtained trans-2-bromocyclohexanecarboxylic acid 10 g (0.048 mol) and ethylenediamine 16 g (0.
27 mol) was placed in a three-necked flask and heated and stirred at 80 ° C. After 3 hours, the pressure was reduced with a vacuum pump to remove excess ethylenediamine, 20 ml of water was added, and the mixture was stirred. The pH was adjusted to 1.5 with concentrated hydrochloric acid, and the precipitated crystals were collected by filtration. After washing with water and drying, intermediate (1) could be obtained. 5.0 g (0.019 mol) of intermediate (1), 9.0 g (0.077 mol) of sodium chloroacetate, and 20 ml of water were placed in a three-necked flask and well stirred in a water bath while maintaining the internal temperature at 80 ° C. The pH was adjusted to 8 to 10 while adding 6.3 g of 49% sodium hydroxide aqueous solution little by little. After the dropping was completed, the mixture was further stirred for 3 hours. Concentrated hydrochloric acid was added to the reaction solution to adjust the pH to 1.3, and the precipitated crystals were collected by filtration and dried. Yield 2.4 g (yield 35%) Compound 14 was obtained from "Journal of the American Chemical Society", Vol. 78, pages 2723 to 2727 (1956) (Journal of the American Chemical Society).
y vol78.2723-2727 (1956)). Other compounds can be similarly synthesized.

The compound represented by the general formula (I) can be applied to any processing composition for processing a silver halide black-and-white light-sensitive material and a silver halide color light-sensitive material. For example, for a silver halide black and white light-sensitive material,
General black-and-white developer, squirrel film infectious developer, fixing solution, washing water, etc.For silver halide color light-sensitive materials, color developing solution, bleaching solution, fixing solution, bleach-fixing solution, adjusting solution, stop solution Examples include, but are not limited to, a hardening solution, a washing water, a stabilizing solution, a rinsing solution, a fogging solution, and a toning solution. The present invention is particularly effective in a black-and-white developing solution, a color developing solution, a fixing solution and a stabilizing solution.
Excellent in color developer.

The amount of the compound represented by the general formula (I) added varies depending on the treatment composition to be added, but it is usually used in the range of 10 mg to 50 g per liter of the treatment composition.

More specifically, for example, when it is added to a black and white developing solution or a color developing solution, the preferable amount is 0.5 to 10 g per liter of the processing solution,
When added to a bleaching solution (eg, hydrogen peroxide, persulfuric acid, bromic acid, etc.), 0.1 to 20 g per liter
1 when added to the fixer or bleach-fixer
It is from 1 to 40 g per liter and, when added to the stabilizing bath, from 50 mg to 1 g per liter. The compounds represented by general formula (I) may be used alone or in combination of two or more.

In the color developing solution and the black and white developing solution, addition of the compound of the present invention can prevent precipitation and improve the stability of the solution. The color developing solution contains a known aromatic primary amine color developing agent. A preferred active ingredient is a p-phenylenediamine derivative, and typical examples thereof are shown below, but the invention is not limited thereto. Typical examples thereof include the following compounds. D-1 4-Amino-3-methyl-N, N-diethylaniline D-2 4-Amino-3-methyl-N-ethyl-N-
β-hydroxyethylaniline D-3 4-amino-3-methyl-N-ethyl-N-
β-methanesulfonamidoethylaniline D-4 4-amino-3-methyl-N-ethyl-N-
β-methoxyethylaniline D-5 4-amino-3-methyl-N-methyl-N-
(3-Hydroxypropyl) aniline D-6 4-amino-3-methyl-N-ethyl-N-
(3-Hydroxypropyl) aniline D-7 4-amino-3-methyl-N-ethyl-N-
(2-Hydroxypropyl) aniline D-8 4-amino-3-ethyl-N-ethyl-N-
(3-Hydroxypropyl) aniline D-9 4-amino-3-methyl-N-propyl-N
-(3-Hydroxypropyl) aniline D-10 4-amino-3-propyl-N-methyl-N
-(3-Hydroxypropyl) aniline D-11 4-amino-3-methyl-N-methyl-N-
(4-Hydroxybutyl) aniline D-12 4-amino-3-methyl-N-ethyl-N-
(4-Hydroxybutyl) aniline D-13 4-amino-3-methyl-N-propyl-N
-(4-Hydroxybutyl) aniline D-14 4-amino-3-methyl-N-ethyl-N-
(3-Hydroxy-2-methylpropyl) aniline D-15 4-amino-3-methyl-N, N-bis (4
-Hydroxybutyl) aniline D-16 4-amino-3-methyl-N, N-bis (5
-Hydroxypentyl) aniline D-17 4-amino-3-methyl-N- (5-hydroxypentyl) -N- (4-hydroxybutyl) aniline D-18 4-amino-3-methoxy-N-ethyl-N
-(4-Hydroxybutyl) aniline D-19 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl) aniline D-20 4-amino-3-propyl-N- (4-hydroxybutyl) Examples include aniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among these, especially 4-amino-3-methyl-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, and their hydrochlorides, p-toluenesulfonates or sulfates are preferred. Also, these p
-Phenylenediamine derivatives are preferably used as salts such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates and the like. The amount of the aromatic primary amine color developing agent used is preferably about 0.01 to 1 liter of the color developing solution.
The concentration is 0.06 molar.

Further, as a preservative for the color developing solution, sodium sulfite, potassium sulfite, sodium bisulfite,
Sulfite salts such as potassium bisulfite, sodium metasulfite and potassium metasulfite, and carbonyl sulfite adducts can be added as necessary. In addition, various hydroxylamines such as those disclosed in JP-A-63-5 as compounds that directly preserve the aromatic primary amine color developing agent.
Compounds described in JP-A Nos. 341 and 63-106655, among which compounds having a sulfo group or a carboxy group are preferable. ) Hydroxamic acids described in JP-A-63-43138, hydrazines and hydrazides described in JP-A-63-146041, 63-44657 and 63-584.
It is preferable to add phenols described in No. 43, α-hydroxyketones and α-aminoketones described in No. 63-44656, and / or various sugars described in No. 63-36244. In addition, in combination with the above compounds, JP-A Nos. 63-4235, 63-24254 and 63-2
1647, 63-146040, 63-278.
41 and 63-25654 and the like, monoamines, 63-30845, 63-14640,
Diamines described in 63-43139 and the like, 63-
21647, 63-26655 and 63-4
4655, polyamines, 63-53551, nitroxy radicals, 63-43140 and 63-53549, alcohols, 63.
-56654 oximes and 63-239
It is preferable to use the tertiary amines described in No. 447.

Other preservatives are disclosed in JP-A-57-441.
48 and 57-53749, various metals, salicylic acids described in JP-A-59-180588,
Alkanolamines described in JP-A-54-3582,
Polyethyleneimines described in JP-A-56-94349, aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544, and the like may be contained as necessary. It is particularly preferable to add an aromatic polyhydroxy compound.

The amount of these preservatives added is such that the color developer 1
0.005-0.2 mol per liter, preferably 0.1.
It is from 01 mol to 0.05 mol.

The color developer used in the present invention has a pH of 9
It can be used in the range of -12 to 12, but preferably 9.
It is 5 to 11.5. The color developing solution may contain compounds of other known developing solution components.

In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of the buffering agent include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate and borophosphate. Potassium salt, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate,
Sodium 5-sulfo-2-hydroxybenzoate (5-
Sodium sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned. However, the present invention is not limited to these compounds.

The amount of the buffering agent added to the color developing solution is 0.1.
It is preferably at least mol / liter, particularly 0.1
It is particularly preferable that the amount is ˜0.4 mol / liter.

In the present invention, various chelating agents can be used in combination as long as the effect of the compound of the present invention is not impaired. The chelating agent is preferably an organic acid compound, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids and phosphonocarboxylic acids. Specific examples include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'.
-Tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid Acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid and the like can be mentioned.

These chelating agents can be used in an amount of, for example, 0.0001 mol to 0.05 mol per liter of the processing liquid.

If necessary, any development accelerator can be added to the color developing solution. As the development accelerator, Japanese Patent Publication Nos. 37-16088, 3-5987, and 38-
7826, 44-12380, 45-9019.
And thioether compounds described in U.S. Pat. No. 3,818,247, JP-A-52-49829 and JP-A-5-49829.
0-15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-30
074, JP-A-56-156826, JP-A-52-43.
429 and the like, quaternary ammonium salts, U.S. Pat. Nos. 2,494,903, 3,128,182, 4,230,796, 3,253,919 and JP-B-41. -11431, U.S. Pat. No. 2,482,54
No. 6, No. 2,496,926, No. 3,582,3
46, etc., amine compounds, JP-B-37-160
88, 42-25201, U.S. Pat. No. 3,12.
No. 8,183, Japanese Patent Publication Nos. 41-11431, 42-2
3883, U.S. Pat. No. 3,532,501, and other polyalkylene oxides, and imidazoles such as 2-methylimidazole and imidazole. It is also preferable to add 1-phenyl-3-pyrazolidones as an auxiliary developing agent for rapid development.

Further, an optional antifoggant can be added to the color developing solution, if necessary. As antifoggant,
Alkali metal halides such as sodium chloride, potassium bromide, potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole,
5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2
Typical examples are nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

Further, the color developing solution may contain a fluorescent whitening agent. As the fluorescent whitening agent, 4,4'-diamino-2,2'-disulfostilbene compound is preferable.
The addition amount is 0 to 5 g / liter, preferably 0.1 g to 4
g / liter. If necessary, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, fatty acid carboxylic acid, aromatic carboxylic acid may be added.

The processing temperature of the color developing solution in the present invention is 20 to 50 ° C, preferably 33 to 55 ° C. Processing time is 30 seconds to 3 minutes 20 for color light-sensitive materials.
Seconds, preferably 1 minute to 2 minutes 30 seconds, and in the case of color print materials, 10 seconds to 1 minute 20 seconds, preferably 20 seconds to 60 seconds.

Various well-known additives which are usually added to the black-and-white first developing solution used for color reversal processing and the black-and-white developing solution of the black-and-white silver halide light-sensitive material in which the compound of the present invention can be used. Can be included.

A typical additive is 1-phenyl-
3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate, potassium bromide and 2-methylbenzimidazole, methyl Examples thereof include inorganic or organic inhibitors such as benzthiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds.

The bleaching solution in which the compound of the present invention can be used contains at least an oxidizing agent for oxidizing silver and a rehalogenating agent (or an alternative organic ligand). As the bleaching agent, known polyaminocarboxylic acid iron (III) complex salts, hydrogen peroxide, persulfates, bromates and the like are used, and they may be used in combination. The amount of the bleaching agent used is 0.05 mol to 2 mol, preferably 0.1 to 5 mol, per liter of the bleaching solution. As the rehalogenating agent, halides such as chloride, bromide and iodide are generally used, but an organic ligand which forms a sparingly soluble silver salt may be used instead of these. Their amount is 0.1 to 2 mol / l, preferably 0.3 to 1.5 mol / l.

The above halide is added as an alkali metal salt or ammonium salt, or a salt of guanidine, amine or the like. Specifically, there are sodium bromide, ammonium bromide, potassium chloride, guanidine hydrochloride and the like, and ammonium bromide is preferable.

The storability of the bleaching solution is improved by adding the compound represented by the general formula (I) and / or (II) to the bleaching solution. Notable with bromate.

The bleach-fixing solution to which the compound of the present invention can be added contains, in addition to the bleaching agent, a fixing agent described later, and if necessary, the rehalogenating agent.
The amount of the bleaching agent in the bleach-fixing solution is the same as that in the bleaching solution. The amount of the rehalogenating agent is 0 to 2.0 mol /
It is 1 liter, preferably 0.01 to 1.0 mol / liter.

Addition of the compound of the present invention to a bleach-fixing solution improves the storability of the solution.

In the bleaching solution or bleach-fixing solution according to the present invention, in addition, 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, a defoaming agent, etc. It is added as needed.

Examples of the bleaching accelerator include US Pat. No. 3,893,858 and German Patent 1,290,81.
No. 2, U.S. Pat. No. 1,138,842, JP-A-53-
95630, Research Disclosure No. 171
No. 29 (1978), a compound having a mercapto group or a disulfide group, a thiazolidine derivative described in JP-A No. 50-140129, US Pat.
Thiourea derivatives described in JP-A-6561, JP-A-49-4
The imidazole compound described in No. 0943, the polyethylene oxides described in German Patent No. 2,748,430, and the polyamine compound described in Japanese Patent Publication No. 45-8836 can be used. Among them, US Patent No. 1,
The mercapto compounds described in 138,842 are preferred.

As the corrosion inhibitor, it is preferable to use nitrates, such as ammonium nitrate and potassium nitrate. The amount added is 0.01 to 2.0 mol / liter, preferably 0.05 to 0.5 mol / liter.

PH of the bleaching solution or bleach-fixing solution of the present invention
Is 2 to 8, preferably 3 to 7.5. When bleaching or bleach-fixing is carried out immediately after color development, the pH of the solution is preferably 6 or less, and preferably 5.5 or less in order to suppress bleaching fog in color photographic materials. In the material for color printing, the pH is preferably in the range of 3 to 7 in order to prevent leuco conversion of the cyan dye.

Therefore, any pH buffer may be used as long as it is not easily oxidized by the bleaching agent and has a buffering action in the above pH range.
For example, organic acids such as acetic acid, glycolic acid, lactic acid, propionic acid, butyric acid, malic acid, chloroacetic acid, levulinic acid, ureidopropionic acid, pyridine, dimethylpyrazole, 2-methyl-o-oxazoline, aminoacetonitril and the like. Examples of organic bases include The amount of these buffers used is 0 to 3 mol / liter, preferably 0.5 to 2
Mol / liter. Also, a plurality of these buffers may be used in combination.

The bleaching or bleach-fixing step is carried out at 30 ° C to 5 ° C.
The temperature range is 0 ° C, preferably 35 ° C to 45 ° C.
Is. The time of the bleaching process is 10 seconds to 5 minutes for the color light-sensitive material, preferably 10 to 60 seconds, and 5 to 70 seconds for the color print light-sensitive material. It is preferably 5 seconds to 60 seconds. Under these preferable processing conditions, good results were obtained quickly and without an increase in stain.

Known fixing agents are used in the fixing solution or the bleach-fixing solution. These are thiosulfates, thiocyanates, thioethers, amines, mercaptos, thiones, thioureas, iodide salts and the like, for example, ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, guanidine thiosulfate, Potassium thiocyanate, dihydroxyethyl-thioether, 3,6-dithia-
Examples include 1,8-octanediol and imidazole. Of these, thiosulfates, particularly ammonium thiosulfate, are preferred for rapid fixing. Further, by using two or more fixing agents in combination, more rapid fixing can be performed. For example, in addition to ammonium thiosulfate, it is also preferable to use the above-mentioned ammonium thiocyanate, imidazole, thiourea, thioether and the like together. In this case, the second fixing agent is 0.01 to 10 with respect to ammonium thiosulfate.
It is preferably added in the range of 0 mol%.

The amount of the fixing agent is the fixing solution or the bleach-fixing solution 1
0.1 mol to 3 mol per liter, preferably 0.5 to
2 mol. The pH of the fixer depends on the type of fixer,
Generally, it is 3 to 9, and particularly when thiosulfate is used, 6.5 to 8 is preferable for obtaining stable fixing performance.

A preservative may be added to the fixing solution and / or the bleach-fixing solution to enhance the stability of the solution over time. For fixers or bleach-fixers containing thiosulfate,
As a preservative, sulfite, and / or hydroxylamine, hydrazine, bisulfite adduct of aldehyde (for example, bisulfite adduct of acetaldehyde, particularly preferably, aromatic aldehyde described in JP-A 1-298935). Bisulfite addition) is effective. Also, JP-A-6
It is also preferable to use the sulfinic acid compound described in 0-283881.

It is also preferable to add a buffer to the fixing solution and / or the bleach-fixing solution in order to keep the pH of the solution constant. For example, phosphate, or imidazole,
1-Methyl-imidazole, 2-methyl-imidazole, imidazoles such as 1-ethyl-imidazole, triethanolamine, N-allylmorpholine, N
-Benzoylpiperazine and the like. In the fixing solution according to the present invention, addition of the compound represented by the general formula (I) and / or (II) improves the storage stability of the solution and also hides iron ions carried from the bleaching solution. The stability of can be improved.

The same effect can be obtained by adding the compound of the present invention to washing water and a stabilizing solution. The washing water or the stabilizing solution used in the washing step may contain various surfactants in order to prevent unevenness of water droplets when the photosensitive material after processing is dried. As these surfactants,
Polyethylene glycol type nonionic surfactant, polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester type anionic surfactant, alkylnaphthalene sulfonate type There are anionic surfactants, quaternary ammonium salt type cationic surfactants, amine salt type cationic surfactants, amino acid type amphoteric surfactants, betaine type amphoteric surfactants, but ionic surfactants are A nonionic surfactant is preferably used because it may combine with various ions mixed with the treatment to form an insoluble substance, and an alkylphenol ethylene oxide adduct is particularly preferable. As the alkylphenol, octyl, nonyl, dodecyl, and dinonylphenol are particularly preferable, and the number of moles of ethylene oxide added is particularly preferably 8 to 14 moles. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

The washing water or stabilizing solution may contain various antibacterial agents and antifungal agents in order to prevent the generation of water stains and the mold generated in the processed light-sensitive material. Examples of these antibacterial agents and antifungal agents include thiazolylbenzimidazole compounds as disclosed in JP-A-57-157244 and JP-A-58-105145, or JP-A-54-27424 and JP-A-54-24424. Kai 57
Of the isothiazolone-based compound shown in No. 8542, the chlorophenol-based compound represented by trichlorophenol, the bromophenol-based compound, the organic tin or the organic zinc compound, the thiocyanic acid or the isothiocyanic acid-based compound. Compound, acid amide compound, diazine or triazine compound, thiourea compound, benzotriazole alkylguanidine compound, quaternary ammonium salt represented by benzalkonium chloride, or penicillin Representative Antibiotics such as Journal Antibacterial and Antifungus Agent (J.Antibact.A
ntifung.Agents) Voll. No. 5, p.207-223 (1
One or more general-purpose antifungal agents described in 983) may be used in combination.

Various bactericides described in JP-A-48-83820 can also be used.

Further, it is preferable to use various chelating agents in combination as long as the effect of the compound of the present invention is not impaired.
Preferred compounds of the chelating agent include aminodicarboxylic acid such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediamine-N, N, N ', N'-.
Examples thereof include organic phosphonic acids such as tetramethylenephosphonic acid, and hydrolyzates of maleic anhydride polymers described in European Patent 345172A1.

Further, it is preferable that the washing water contains a preservative which may be contained in the fixing solution or the bleach-fixing solution.

Examples of the stabilizing solution include organic acids and pH 3
A liquid having a buffering capacity of ˜6, an aldecht (eg, formalin or glutaraldehyde), hexamethylenetetramine, hexahydrotriazine, a liquid containing an N-methylol compound (eg, dimethylolurea, N-methylolpyrazole). In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners,
Hardeners and alkanolamines described in US Pat. No. 4,786,583 can be used.

The washing step and the stabilizing step are preferably a multi-stage countercurrent system, and the number of stages is preferably 2 to 4. The replenishment amount is 2 to 30 of the amount brought in from the previous bath per unit area.
Times, preferably 2 to 15 times.

As the water used in the washing step or the stabilizing step, tap water, water deionized to a Ca or Mg concentration of 5 mg / liter or less with an ion exchange resin, halogen, an ultraviolet germicidal lamp, etc. It is preferred to use more pasteurized water.

As the water for correcting the evaporation, tap water may be used, but deionized water or sterilized water which is preferably used in the above washing step or stabilizing step is used. Is good.

In each processing solution of the present invention, it is preferable that the processing solution is agitated as much as possible. As a method for strengthening stirring, a method of causing a jet stream of a processing solution to collide with an emulsion surface of a light-sensitive material described in JP-A-62-183460, or a stirring means using a rotating means described in JP-A-62-18346. To increase the stirring effect by moving the photosensitive material while contacting the emulsion surface with a wiper blade or a squeeze roller provided in the solution to make the emulsion surface turbulent. There is a method of increasing the circulation flow rate.

The processing method of the present invention is preferably carried out using an automatic processor. Regarding the conveying method in such an automatic developing machine, see JP-A-60-191257, 60.
No. 191258 and No. 60-191259. Further, in order to perform rapid processing using the processing composition of the present invention, it is preferable to shorten the crossover between processing tanks in an automatic processor. Crossover time is 1
Japanese Patent Laid-Open No. 1-319 discloses an automatic processor having a time of 0 seconds or less.
No. 038.

When continuous processing is performed by using the automatic developing machine according to the processing method of the present invention, consumption of processing liquid components accompanying the processing of the light-sensitive material is supplemented, and undesirable components eluted from the light-sensitive material are removed. In order to suppress the accumulation in the processing liquid, it is preferable to add a replenishing liquid according to the amount of the processed light-sensitive material.
Further, two or more processing baths may be provided in each processing step, and in that case, it is preferable to adopt a countercurrent system in which the replenisher is poured from the rear bath to the front bath. In particular, it is preferable to use a cascade of 2 to 4 stages in the washing process and the stabilizing process.

The amount of the replenishing solution is preferably reduced as long as the compositional change in each processing solution does not cause a problem of photographic performance or other contamination of the solution.

The amount of the color developing replenisher is 100 ml to 1500 ml, preferably 100 ml to 1000 ml per 1 m ² of the light-sensitive material in the case of a color photographic material, and ²⁰ ml per m ² of the light-sensitive material in the case of a color print material. 220 ml, preferably 30-160 ml.

The amount of the bleach replenisher is, in the case of a color photographic material, 10 ml to 500 ml, preferably 10 ml to 160 ml, per 1 m ^{2 of} the light-sensitive material. In the case of color print materials, ²⁰ ml to 300 ml per 1 m ^{2 of} light-sensitive material, preferably 5
It is 0 ml to 150 ml.

The amount of the bleach-fixing replenisher is 100 ml to 3000 ml, preferably 200 ml to 1300 ml per 1 m ^{2 of} the light-sensitive material in the case of the color photographic material, and ²⁰ ml per m ² of the light-sensitive material in the case of the color print material. It is 300 ml, preferably 50 to 200 ml. The bleach-fixing solution may be replenished as a single solution, or as a bleaching composition separately as a fixing composition, and a bleaching bath and / or
Alternatively, a bleach-fixing replenisher may be prepared by mixing an overflow solution from the fixing bath.

The amount of the fixing replenisher is 300 ml to 3000 ml, preferably 300 ml to 1000 ml per 1 m ^{2 of} the light-sensitive material in the case of the color photographic material, and ²⁰ ml to 300 ml per 1 m ^{2 of} the light-sensitive material in the case of the color print material. It is preferably 50 ml to 200 ml.

The replenishing amount of the washing water or the stabilizing solution is 1 to 30 times, and more preferably 2 to 15 times, the amount carried in from the previous bath per unit area.

In order to further reduce the amount of the replenisher for environmental protection, it is also preferable to use various regenerating methods in combination. Regeneration may be performed while circulating the processing solution in the automatic processor, or after removing the processing solution from the processing tank, performing appropriate recycling processing and returning it to the processing tank as a replenishing solution again. Is also good.

Regeneration of the developer is carried out by ion exchange treatment with anion exchange resin, removal of accumulated substances by electrodialysis treatment,
And / or the addition of chemicals called regenerants. The regeneration rate is preferably 50% or more, 70
% Or more is more preferable. As the anion exchange resin, a commercially available one can be used, but it is also preferable to use the highly selective ion exchanger described in JP-A No. 63-11005.

The metal chelate-type bleaching agent in the bleaching solution and / or the bleach-fixing solution becomes in a reduced state with the bleaching treatment. Accumulation of this reduced metal chelate not only deteriorates the bleaching performance, but in some cases, the image dye becomes a leuco dye, which causes a decrease in image density. Therefore, it is preferable that the bleaching solution and / or the bleach-fixing solution be subjected to a continuous regeneration method in cooperation with the processing. Specifically, it is preferable to blow air into the bleaching solution and / or the bleach-fixing solution with an air pump to reoxidize the reduced metal chelate with oxygen. In addition, it can be regenerated by adding an oxidizing agent such as hydrogen peroxide, persulfate or bromate.

Regeneration of the fixing solution and the bleach-fixing solution is performed by electrolytically reducing accumulated silver ions. In addition, it is also preferable to remove accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance. Ion exchange or ultrafiltration is used to reduce the amount of washing water used, and it is particularly preferable to use ultrafiltration.

The photographic light-sensitive material which can be processed with the processing composition of the present invention includes a usual black-and-white silver halide photographic light-sensitive material (for example, black-and-white light-sensitive material for photographing, black-and-white light-sensitive material for X ray, black-and-white light sensitive material for printing). Material), a normal multilayer silver halide color photographic light-sensitive material (for example, a color negative film, a color reversal film, a color positive film,
Film color negative film, color photographic paper, reversal color photographic paper, direct positive color photographic paper), infrared light sensitive material for laser scanner, diffusion transfer photosensitive material (eg silver diffusion transfer photosensitive material, color diffusion transfer photosensitive material) And so on.

The photographic light-sensitive material according to the present invention has various layer constitutions (for example, a silver halide emulsion layer, an undercoat layer and a halation layer having a sensitivity to red, green and blue, respectively) on one side or both sides depending on the purpose of the light-sensitive material. Prevention layer, filter layer,
It may be an intermediate layer, a surface protective layer) or an array.

Support of photographic light-sensitive material according to the present invention; coating method; kind of silver halide used in silver halide emulsion layer, surface protective layer, etc. (eg, silver iodobromide, silver iodochlorobromide, odor) Silver halide, silver chlorobromide, silver chloride), its particle shape (eg, cubic, tabular, spherical), its particle size, its variation rate, its crystal structure (eg, core / shell structure, multiphase structure, homogeneous phase) Structure), its manufacturing method (for example, single jet method, double jet method, binder (for example, gelatin), hardener, antifoggant, metal doping agent, silver halide solvent, thickener, emulsion precipitant, size) Stabilizers, anti-adhesion agents, stabilizers, anti-staining agents, dye image stabilizers, anti-stain agents, chemical sensitizers, spectral sensitizers, sensitivity enhancers, supersensitizers, nucleating agents, couplers (eg, , Pivaloyl acetanilide type and benzo Le acetanilide type yellow couplers, 5-pyrazolone type and pyrazoloazole type magenta coupler, phenol type and naphthol type cyan couplers, DIR couplers, bleach accelerator-releasing couplers,
Competitive couplers, colored couplers), coupler dispersion methods (for example, oil-in-water dispersion method using high boiling point organic solvent), plasticizers, antistatic agents, lubricants, coating aids, surfactants, brighteners, formalin Scavenger, light scattering agent,
Matting agent, light absorber, ultraviolet absorber, filter dye,
Irradiation dyes, development improvers, matting agents, preservatives (for example, 2-phenoxyethanol), antifungal agents, etc. are not particularly limited. For example, Product Licensing 92, 107-110 (1971). December) and Research Disclosure (hereinafter referred to as RD) No. 1
7643 (December 1978), RD magazine No. 18716.
(November 1979), RD magazine No. 307105 (19)
The description of November 1989) can be referred to.

The photographic light-sensitive material according to the present invention may contain a developing agent. As a developing agent that can be contained in the light-sensitive material, RD magazine No. 17643, page 29, "De
The ones described in the section “veloping agents” can be mentioned. In particular, hydroquinone and pyrazolidones are preferably used.

The photographic light-sensitive material according to the present invention may use a coupler which develops yellow, cyan and magenta as described above, and the above-mentioned RD magazine No. 17643, VII-C.
To G, various couplers described in the patents described in RD-No. 307105, VII-C to G, and Japanese Patent Laid-Open No.
2-215272 is mentioned in detail.

[0118]

The present invention will be described below with reference to examples.
The present invention is not limited to these. Example 1 Preparation of Multilayer Color Photosensitive Material Each layer having the composition shown below was applied to prepare a multilayer color photosensitive material A01. (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 Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.60 ExM-1 0.11 ExF-1 3.4 × 10 ^-3 ExF-2 (solid disperse dye) 0.03 ExF-3 (solid disperse dye) ) 0.04 HBS-1 0.16

Second layer (intermediate layer) ExC-2 0.055 UV-1 0.011 UV-2 0.030 UV-3 0.053 HBS-1 0.05 HBS-2 0.02 Polyethyl acrylate latex 8.1 × 10 ^-2 gelatin 1.75

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion A Silver 0.46 ExS-1 5.0 × 10 ^-4 ExS-2 1.8 × 10 ^-5 ExS-3 5.0 × 10 ^-4 ExC-1 0.11 ExC-3 0.045 ExC-5 0.0050 ExC-7 0.001 ExC-8 0.010 Cpd-2 0.005 HBS-1 0.090 Gelatin 0.87

Fourth Layer (Medium-Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.70 ExS-1 3.0 × 10 ^-4 ExS-2 1.2 × 10 ^-5 ExS-3 4.0 × 10 ^-4 ExC-1 0.22 ExC-2 0.055 ExC-5 0.007 ExC-8 0.009 Cpd-2 0.036 HBS-1 0.11 Gelatin 0.70

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion E Silver 1.62 ExS-1 2.0 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 3.0 × 10 ^-4 ExC-1 0.133 ExC-3 0.040 ExC-6 0.040 ExC-8 0.014 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 0.85

6th layer (intermediate layer) Cpd-1 0.07 ExF-4 0.03 HBS-1 0.04 polyethyl acrylate latex 0.19 gelatin 2.30

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide Emulsion A Silver 0.24 Silver iodobromide Emulsion B Silver 0.10 Silver iodobromide Emulsion C Silver 0.14 ExS-4 4.0 × 10 ^-5 ExS-5 1.8 × 10 ^-4 ExS-6 6.5 × 10 ^-4 ExM-1 0.005 ExM-2 0.30 ExM-3 0.09 ExY-1 0.015 HBS-1 0.26 HBS-3 0.006 Gelatin 0.80

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.94 ExS-4 2.0 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 5.4 × 10 ^-4 ExM-2 0.16 ExM-3 0.045 ExY-1 0.008 ExY-5 0.030 HBS-1 0.14 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E Silver 1.29 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-4 0.011 ExM-1 0.016 ExM-4 0.046 ExM-5 0.023 Cpd-3 0.050 HBS-1 0.20 HBS-2 0.08 Polyethyl acrylate latex 0.26 Gelatin 0.82

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.010 Cpd-1 0.10 ExF-5 (solid disperse dye) 0.06 ExF-6 (solid disperse dye) 0.06 ExF-7 (oil-soluble dye) 0.005 HBS-1 0.055 Gelatin 0.70

Eleventh layer (low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide emulsion C Silver 0.25 Silver iodobromide emulsion D Silver 0.10 ExS-7 8.0 × 10 ^-4 ExY-1 0.010 ExY-2 0.70 ExY-3 0.055 ExY-4 0.006 ExY-6 0.075 ExC-7 0.040 HBS-1 0.25 Gelatin 1.60

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion F Silver 1.30 ExS-7 3.0 × 10 ^-4 ExY-2 0.15 ExY-3 0.06 HBS-1 0.070 Gelatin 1.13

Thirteenth layer (first protective layer) UV-2 0.08 UV-3 0.11 UV-4 0.26 HBS-1 0.09 Gelatin 1.20

14th layer (second protective layer) Silver iodobromide emulsion G Silver 0.10 H-1 0.30 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.75

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B are appropriately added. -6,
F-1 to F-17 and iron salts, lead salts, gold salts, platinum salts,
It contains iridium salt, palladium salt, and rhodium salt.

[0134]

[Table 1]

In Table 1, (1) Emulsions A to F were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to F were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples 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.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of 5% aqueous solution of sodium p-octylphenoxyethoxyethane sulfonate and 0.5 g of 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) and 0.5 g were put into a 700 ml pot mill, and dye ExF- 5.0 g of 2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. For this dispersion, a BO type vibrating boat mill manufactured by Chuo Koki was used. After dispersion, take out the contents, 12.5%
Add to 8 g of gelatin aqueous solution, filter out beads,
A gelatin dispersion of the dye was obtained. The average particle size of the dye fine particles was 0.44 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle size of the fine dye particles is 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
It was m. ExF-5 is a European patent application publication (EP)
The particles were dispersed by the microprecipitation dispersion method described in Example 1 of the specification of No. 0,549,489A. The average particle size was 0.06 μm.

[0138]

[Chemical 19]

[0139]

[Chemical 20]

[0140]

[Chemical 21]

[0141]

[Chemical formula 22]

[0142]

[Chemical formula 23]

[0143]

[Chemical formula 24]

[0144]

[Chemical 25]

[0145]

[Chemical formula 26]

[0146]

[Chemical 27]

[0147]

[Chemical 28]

[0148]

[Chemical 29]

[0149]

[Chemical 30]

[0150]

[Chemical 31]

[0151]

[Chemical 32]

[0152]

[Chemical 33]

[0153]

[Chemical 34]

[0154]

[Chemical 35]

[0155]

[Chemical 36]

A processing solution was prepared below.

(Color Developer) Unit (g) Diethylenetriaminepentaacetic acid 1.2 Compound of Table 2 0.01 mol Caustic potassium 2.50 Sodium sulfite 3.84 Sodium bicarbonate 1.8 Potassium carbonate 31.7 Potassium bromide 5 .60 Potassium iodide 1.3 mg Hydroxylamine sulfate 2.5 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 9.0 Water was added to 1.0 liter. pH 10.05

(Bleach-fixing solution)
Unit (g) 1.8 mol of fixing agent (compound A)

[0159]

[Chemical 37]

1,3-Propanediaminetetraacetic acid Ferric ammonium monohydrate 144.0 Ammonium bromide 40.0 Ammonium nitrate 20.0 Water was added to 1.0 liter pH (25 ° C.) 4.5 (acetic acid and (Adjust with ammonium water)

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and an OH-type strongly basic anion exchange resin (Amberlite IRA-400) are passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3
Treatment to less than mg / l, followed by 20 mg / l sodium dichloride isocyanate and sodium sulphate 15
0 mg / l was added. The pH of this solution is 6.5-
It was in the range of 7.5.

(Stabilizer) For Application (Unit g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 1.0 liter with addition of water pH 5.0-8.0

Ferric chloride (5 ppm) as ferric ion and calcium nitrate (150 ppm as calcium ion) were added to the above color developing solution to prepare samples 101 to 115 as circulation type liquid aging tester with opening ratio of 0.05 cm ^-1. At 45
Aged at 7 ° C for 7 days. Next, 35m created above
White light (color temperature of light source 4
A wedge exposure of 800 ° K) was applied. After the exposure, the samples 101 to 115 prepared as described above were processed in the following steps using a color developing solution immediately after preparation and a color developing solution aged. Processing process (Process) (Processing time) (Processing temperature) Color development 1 minute 50 seconds 45 ℃ Bleaching fixing 1 minute 50 seconds 45 ℃ Washing with water (1) 15 seconds 45 ℃ Washing with water (2) 15 seconds 45 ℃ Washing with water (3) 15 seconds 45 ℃ Washed with water (4) 15 seconds 45 ℃ Washed with water (5) 15 seconds 45 ℃ Stabilized 2 seconds Room temperature Dry 50 seconds 70 ℃

The density decrease (ΔD _max ) of the G density with each lapse of time was determined on the basis of the maximum density when processed with a novel color developing solution (fresh solution). Further, the residual ratio of the developing agent and hydroxylamine after aging was determined by analysis.
Further, with respect to the color developing solution after the passage of time, the occurrence of tar on the liquid surface was checked visually. The results are summarized in Table 2.

[0165]

[Table 2]

[0166]

[Chemical 38]

As is clear from Table 2, when the chelate compound is not added and when the conventional chelating agent is added, the tar generation is prevented and the liquid stability is not sufficiently secured. It can be seen that a great effect is obtained only by adding the compound of the invention.

Example 2 The bleach-fixing solution used in Example 1 was tested by changing it to the following composition. As in Example 1, the addition of the compound of the present invention prevented tar from occurring and the stability of the solution. The security has reached a sufficient level. (Bleach-fixing solution) Mother liquor (mol) Ferric ammonium salt of the compound represented by the formula B 0.17

[0169]

[Chemical Formula 39]

Nitric acid 0.15 Ammonium thiosulfate 1.25 Ammonium sulfite 0.10 Metacarboxybenzenesulfinic acid 0.05 Water was added to 1.0 liter pH (adjusted with acetic acid and ammonia) 5.8

[0171]

The processing solution of the present invention is a processing for a silver halide light-sensitive material in which a decrease in color density with the passage of time is small, a developing agent and hydroxylamine are highly retained, and a tar on the liquid surface is little generated. Excellent as a liquid.

Claims (2)

[Claims] 1. A processing composition for a silver halide photographic light-sensitive material, comprising a compound represented by the following general formula (I). General formula (I) (In the formula, X represents a cycloaliphatic group. X ₁ and X ₂ each represent a hydrogen atom, -L ₁ -A ₂ or a cycloaliphatic group. L represents a divalent aliphatic group. L ₁ Represents an alkylene group, and A ₁ and A ₂ are -COOM, -OH,-, respectively.
It represents SO ₃ M or —PO (OM) ₂ . M represents a hydrogen atom or a cation. W represents a divalent linking group containing a divalent aliphatic group and / or an arylene group. ) 2. A silver halide photographic light-sensitive material, characterized in that the image-wise exposed silver halide photographic light-sensitive material is treated with a processing liquid containing at least one compound represented by the following formula (I). Processing method. General formula (I) (In the formula, X represents a cycloaliphatic group. X ₁ and X ₂ each represent a hydrogen atom, -L ₁ -A ₂ or a cycloaliphatic group. L represents a divalent aliphatic group. L ₁ Represents an alkylene group, and A ₁ and A ₂ are -COOM, -OH,-, respectively.
It represents SO ₃ M or —PO (OM) ₂ . M represents a hydrogen atom or a cation. W represents a divalent linking group containing a divalent aliphatic group and / or an arylene group. )