JP2003084406A - Silver halide color photographic processing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic processing agent comprising a photographic processing composition and a container containing this composition and practical also in terms of production and capable of preventing lowering of bleaching performance by suppressing precipitation in the photographic processing composition in the container with age. SOLUTION: In the silver halide color photographic processing agent comprising a photographic processing composition and a container containing this composition, the container is made of plastic based on polylactic acid or cellulose acetate and the photographic processing composition contains a bleaching agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic processing agent,
More specifically, it relates to a photographic processing agent comprising a silver halide photographic processing composition and a container enclosing the photographic processing composition.

[0002]

2. Description of the Related Art A processing solution for a silver halide color photographic light-sensitive material is stored in various containers not only during the distribution process from the manufacturer's shipment to the delivery to the user, but also during the user's storage. As a container for the processing solution of the silver halide color photographic light-sensitive material, a hard container such as PET (polyethylene terephthalate), vinyl chloride or glass is used when the color developing solution which is easily oxidized is contained therein. When a liquid having a bleaching ability excellent in oxidation resistance (a bleaching liquid or a bleach-fixing liquid) is housed inside, a polyethylene container is generally used.

Due to the recent spread of over-the-counter processing and close-up of environmental problems, rapid processing and reduction of replenishment amount have become more important issues, and in order to achieve these, each processing solution is highly active. Came to be used. There is a similar tendency for a liquid having a bleaching ability such as a bleaching liquid, and when a liquid having such a highly active bleaching ability is stored for a long time in a conventional polyethylene container, it precipitates on the bottom of the container over time. In some cases, problems such as desilvering failure and color restoration failure (leuco conversion of cyan dye) may occur when processing is performed using such a solution, and improvement thereof has been long sought.

This is because iron (III) aminopolycarboxylate, which is a bleaching agent, decomposes aminopolycarboxylic acid by self-decomposition due to lack of oxygen inside the container, and the concentration of iron (II) aminopolycarboxylate increases. Unstable iron (II) is Fe
It is presumed that, as (OH) ₂ (ferric hydroxide) precipitates, the bleaching ability decreases, leading to poor desilvering and poor color restoration.

In particular, when the bleaching composition is stored in a polyethylene container at a high temperature (for example, 30 ° C. or higher) for a long time (for example, from half a month to one year), the above phenomenon remarkably occurs. Liquids often give a 2 year warranty,
In Southeast Asia, etc., it reaches a high temperature of over 30 ℃,
This was a problem.

[0006]

In a container containing a bleaching agent composition, it is conceivable to reduce the thickness of the container in order to prevent the occurrence of an oxygen deficiency inside, but it is possible to simply reduce the thickness of the container. If the thickness is reduced, the strength is insufficient, and it is not possible to comply with so-called UN regulations (export dangerous goods transportation regulations) and toxic poison transportation regulations. As another means, it is conceivable to provide a large number of small protrusions on the container to increase the surface area so that more air can be taken into the container. Occurs, and the reaction between the internal processing liquid and the external air is hindered. In addition, the strength of the protruding portion was insufficient and it was sometimes damaged. In order to eliminate this inconvenience, Japanese Unexamined Patent Publication No. 7-5638 discloses that the surface area is large,
Also disclosed is a container having an accordion-type device wall in which bubbles are not generated in the container. This container represents one solution, but with further improvements in storage stability,
It is desired that the container can be easily manufactured.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to prevent precipitation of the photographic processing composition in a container from occurring over time and to prevent a decrease in bleaching ability. Another object of the present invention is to provide a photographic processing agent comprising a photographic processing composition and a container which is also practical from the viewpoint of manufacturing the photographic processing composition.

[0008]

As a result of earnest research, the present inventor has found that the above problems can be solved by using a specific container material, and has arrived at the present invention based thereon. That is, the present invention is as follows.

1. A photographic processing agent comprising a photographic processing composition and a container enclosing the photographic processing composition, wherein the container is made of a plastic whose main component is polylactic acid or cellulose acetate, and A silver halide color photographic processing agent, wherein the photographic processing composition is a photographic processing composition containing a bleaching agent.

2. 2. The silver halide color photographic processing agent as described in 1 above, wherein the bleaching agent contains at least one kind of aminopolycarboxylic acid iron (III) complex.

3. 3. The silver halide color photographic processing agent as described in 1 or 2 above, wherein the bleaching agent further contains at least one compound represented by the following general formula (A). In formula ^{_{(A) A 5 (-COOM 5}} ) n 6 Formula (A), A ₅ represents a n _6-valent organic radical, n
₆ represents an integer of 1 to 3. When n ₆ = 1, A ₅ represents an alkyl group or a phenyl group, when n ₆ = 2, A ₅ represents a single bond or a divalent linking group, and when n ₆ = 3, A ₅ represents a trivalent organic group. Represents a group. M ⁵ represents an ammonium group, an alkali metal atom or a hydrogen atom.

[0012]

The present invention will be described below. The photographic processing composition constituting the photographic processing agent according to the present invention may be any processing solution containing a bleaching agent and having a bleaching ability, and preferably a bleaching solution or a bleach-fixing solution.

As the bleaching agent contained in these processing solutions, aminopolycarboxylic acid iron (III) complexes are preferable.
Specific examples of the aminopolycarboxylic acid forming the aminopolycarboxylic acid iron (III) complex include those represented by the following general formula (I):
The compound represented by General formula (II) and General formula (III) can be mentioned. These iron (III) complexes may form salts with sodium, potassium, ammonium, lithium, etc., but in the description of the present specification, in principle, the above aminopolycarboxylic acid and its salt are in acid form, That is, it is represented by aminopolycarboxylic acid. General formula (I)

[0014]

[Chemical 1]

In the general formula (I), A ₁ , A ₂ , A ₃ and A ₄ each represent --CH ₂ OH, --PO ₃ (M ² ) ₂ or --COOM ¹ .
They may be the same or different. M ¹ and M ² represent a hydrogen atom, an alkali metal atom, an ammonium group or an organic ammonium group. X is a linear or branched alkylene group having 2 to 6 carbon atoms, a divalent organic radical, saturated or unsaturated to form a ring, or _{- (B 1 O) n 5} -B 2 - represents a. n ₅ represents an integer of 1 to 8, and B ₁ and B ₂ may be the same or different and each represents an alkylene group having 1 to 5 carbon atoms. n ₁ , n ₂ , n ₃ and n ₄ represent an integer of 1 or more and 10 or less,
They may be the same or different. General formula (II)

[0016]

[Chemical 2]

In the general formula (II), R ₁ , R ₂ , R ₃ , R ₄ ,
R ₅ , R ₆ , R ₇ and R ₈ are each a hydrogen atom, an alkyl group,
Represents an aromatic group or a hydroxy group. W has 3 to 3 carbon atoms
10 represents a divalent linking group. X ₁ and X ₂ each represent a hydrogen atom, an alkyl group, a hydroxyalkyl group or an alkoxyalkyl group. M ¹ , M ² , M ³ and M ⁴ represent a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an onium group. t and u are 1 or 0.

General formula (III) R ₃₁ R ₃₂ R ₃₃ N In the general formula (III), R ₃₁ , R ₃₂ and R ₃₃ may be the same or different and each is a hydrogen atom, an alkyl group or an alkoxyalkyl group. Represents a group, a carboxyalkyl group, a hydroxyalkyl group, and a carboxyalkylaminoalkyl group. Moreover, the total sum of the carboxyl groups contained in R ₃₁ , R ₃₂ and R ₃₃ is 2 or more.

Hereinafter, the above general formulas (I), (II) and (II
I) will be explained in detail in order. First, general formula (I)
The compound represented by will be described. In formula (I), A _{1 to} A ₄ may be the same or different and each represents —CH ₂ OH, —PO ₃ (M ² ) ₂ or —COOM ¹ . M ¹ ,
M ² is a hydrogen atom, an alkali metal atom (for example, sodium,
Potassium, etc.), ammonium group or organic ammonium group (eg, methylammonium, trimethylammonium, etc.).

X represents a linear or branched alkylene group having 3 to 6 carbon atoms, a saturated or unsaturated organic group forming a ring, or-(B ₁ O) n ₅ B _2- . B ₁ and B ₂ may be the same or different and each represents an alkylene group having 1 to 5 carbon atoms (including a substituent). n _{1 to} n ₄ represent integers of 1 or more and 10 or less, which may be the same or different, and at least one is 2 or more. Examples of the alkylene group represented by X include ethylene, trimethylene, tetramethylene and the like. Further, examples of the alkylene group represented by B ₁ and B ₂ include methylene, ethylene, trimethylene and the like. Examples of the substituent of the alkylene group represented by X, B ₁ or B ₂ include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group, etc.). n ₅ is 1 to
It represents an integer of 8, preferably 1 to 4, and particularly preferably 1 to 2.

Specific preferred examples of the compound represented by the above general formula [I] are shown below, but the invention is not limited thereto.

[0022]

[Chemical 3]

[0023]

[Chemical 4]

[0024]

[Chemical 5]

[0025]

[Chemical 6]

[0026]

[Chemical 7]

The above compounds (I-11), (I-12),
(I-13), (I-14), and (I-15) may include both cis isomers and trans isomers, or one of them.

The compound represented by the above general formula [I] can be synthesized by a generally known method. The general synthesis method is described in, for example, Chelate Chemistry (5), edited by Keihei Ueno, Nankodo page 311 (synthesis of ethylenediamine-N, N'-disuccinic acid), Inorgnic Chemistry, 7, 2405 (1968).

Particularly preferred compounds among the specific examples are (I
-3), (I-4), (I-11), (I-16), (I-
28) and (I-30).

In the present invention, the iron (III) complex salt of the compound represented by the general formula (I) is preferably a complex in which the stoichiometric ratio of the iron (III) ion to the general formula (I) is 1: 1. Further, an amine, a thiocyanic acid group, a cyanate group or the like may be coordinated, and the positive or negative valence is neutralized by the water-soluble cation or anion. Further, it may be further hydrated.

Next, the compound of the general formula (II) will be described. In the general formula (II), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ , R ₇ and R ₈ are each a hydrogen atom, an alkyl group, an aromatic group or a hydroxy group, and when these groups represent an alkyl group, the alkyl group may be linear, branched or cyclic. Any of these may be used, and those having 1 to 10 carbon atoms are preferable. A straight-chain alkyl group is more preferable, a C1-C3 alkyl group is still more preferable, and a methyl group and an ethyl group are particularly preferable.
When R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ represent an aromatic group, the aromatic group is a monocyclic or bicyclic aryl group or an aromatic heterocycle. Examples of the group include a phenyl group, a naphthyl group and a pyridyl group, and a phenyl group is more preferable.

These R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and
The alkyl group and aromatic group represented by R ₈ may have a substituent, and when the substituent is an alkyl group, it has 1 carbon atom.
To 20, preferably 1 to 10 carbon atoms, more preferably 1
To 4 linear, branched or cyclic alkyl groups such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group and lauryl group. A group, a stearyl group, a cyclohexyl group, and a 2-ethylhexyl group. When the substituent is an aryl group,
An aryl group having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms, and more preferably 6 to 8 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a cresyl group. When the substituent is an amino group, the substituent is an amino group having 0 to 20 carbon atoms, preferably 0 to 10 carbon atoms, more preferably 0 to 6 carbon atoms, and examples thereof include an amino group, a methylamino group and dimethylamino. Group, diethylamino group, dibutylamino group, dioctylamino group. When the substituent is an alkoxy group, it is an alkoxy group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, for example, a methoxy group, an ethoxy group, a butoxy group, a propoxy group,
A lauryloxy group is mentioned. When the substituent is an aryloxy group, it has 6 to 12 carbon atoms, preferably 6 to 1 carbon atoms.
0, more preferably an aryloxy group having 6 to 8 carbon atoms, and examples thereof include a phenoxy group and a tolyloxy group. When the substituent is an acyl group, it is an acyl group having 2 to 12 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and examples thereof include an acetyl group and a propanoyl group. 2 carbon atoms when the substituent is an alkoxycarbonyl group
To 12, preferably 2 to 10 carbon atoms, and more preferably 2 to 8 carbon atoms, and examples thereof include a methoxycarbonyl group.

As other substituents, an aryloxycarbonyl group (having 7 to 20 carbon atoms, preferably 7 to 20 carbon atoms)
15, particularly preferably having 7 to 10 carbon atoms, such as a phenyloxycarbonyl group), an acyloxy group (having 2 to 12 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms), for example acetoxy. Group), an acylamino group (having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, for example, an acetylamino group), an alkoxycarbonylamino group (having 2 to 1 carbon atoms).
2, preferably 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, such as a methoxycarbonylamino group),
Aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms, particularly preferably 7 to 10 carbon atoms, for example, phenyloxycarbonylamino group), sulfonylamino group (having 1 to 12 carbon atoms). 1
0, preferably 1 to 6 carbon atoms, more preferably 1 carbon atoms
To 4 and, for example, a methanesulfonylamino group) and a sulfamoyl group (having 0 to 10 carbon atoms, preferably 0 to 10 carbon atoms).
6, more preferably 0 to 4, for example, a sulfamoyl group, a methylsulfamoyl group), a carbamoyl group (having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, For example, a carbamoyl group, a methylcarbamoyl group), an alkylthio group (having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, for example, a methylthio group, an ethylthio group, a carboxymethylthio group), arylthio Group (C6-20, preferably C6-10, more preferably C6-8
And, for example, a phenylthio group), a sulfonyl group (having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, for example, methanesulfinyl group), a ureido group (having 1 to 8 carbon atoms). , Preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, for example, a ureido group,
And a methylureido group), a hydroxy group, a mercapto group, a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, and a heterocyclic group (for example, an imidazolyl group and a pyridyl group). If possible, it may be a dissociation product or a salt thereof. These substituents may be further substituted with the above-mentioned substituents.

Preferably, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇
And R ₈ is a hydrogen atom or a hydroxy group. More preferably, R ₁ , R ₂ , R ₃ , R ₅ , R ₆ and R ₇ are hydrogen atoms, and R ₄ and R ₈ are hydrogen atoms or hydroxy groups. Most preferably, R _{1 to} R ₈ are all hydrogen atoms.

In the general formula (II), the divalent linking group represented by W can be preferably represented by the following general formula (W). Formula _{(W) - (W 1 -D} ) m- (W 2) n- In formula (W), W ₁ and W ₂ may be different even in the same, the sum of carbon atoms 3 10 to 10, and a preferable linking group is a linear or branched alkylene group having 3 to 8 carbon atoms (for example, n-propylene group, i-propylene group, i-butylene group, 1,2-
Hexylene group, 3-ethylhexylene group), carbon number 5
10 cycloalkylene groups (for example, 1,2-cyclohexylene group, 1,4-cyclohexylene group), 6 to 6 carbon atoms
10 arylene groups (eg 1,2-phenylene group,
1,4-o-tolylene group), an aralkylene group having 7 to 10 carbon atoms (for example, an o-xylenylene group, a 2,2-phenylene group) or a carbonylene group.

D represents --O--, --S--, --N (Rw)-or a divalent nitrogen-containing heterocyclic group, preferably --O-- or --S.
-, -N (Rw)-. Rw is a hydrogen atom or -CO
OMa, -PO ₃ MbMc, -OH or -SO ₃ Md
An alkyl group having 1 to 8 carbon atoms which may be substituted with (for example, a methyl group, a butyl group, a hexyl group) or a carbon number of 6 to
10 aryl groups (eg phenyl, tolyl, 2-
Represents an ethylphenyl group). Preferably Rw has 1 carbon atom
~ 8 alkyl groups.

The connecting group represented by W has a total carbon number of W of 1
It may have a substituent within the range of 0, and examples of the substituent include the substituents described above as the groups which may be substituted by the alkyl group represented by R _{1 to} R ₈ or the aromatic group. The divalent nitrogen-containing heterocyclic group is preferably a 5- or 6-membered ring in which the heteroatom is nitrogen, and a group which is connected to W ₁ and W _{2 by} adjacent carbon atoms such as imidazolyl group is preferable. More preferable. Preferable W ₁ and W ₂ include an alkylene group having 2 to 4 carbon atoms.

Ma, Mb, Mc and Md each represent a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an onium group. The alkali metal atom is a metal atom such as lithium, sodium or potassium, the alkaline earth metal atom is a metal atom such as calcium or magnesium, and the onium group is an ammonium group (for example, ammonium group, tetraethylammonium group) or pyridinium. A group etc. can be mentioned.

M represents an integer of 0 to 3, and when m is 2 or 3, W ₁ -D may be the same or different.
m is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0. n represents an integer of 1 to 3, n is 2 or 3
Then W ₂ may be the same or different. n is preferably 1 or 2, with 1 being particularly preferred. Specific examples of W include the following.

[0040]

[Chemical 8]

[0041]

[Chemical 9]

The alkyl group (unsubstituted) represented by X ₁ and X ₂ represents a linear or branched alkyl group having 1 to 5 carbon atoms.
More preferred ₂ °, preferably a linear alkyl group, more preferably a methyl group or an ethyl group. The alkoxyalkyl group represented by X ₁ and X ₂ preferably has an alkoxy group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms. More preferably, the alkoxy group has 1 to 3 carbon atoms and the alkyl group has 1 to 3 carbon atoms. Specific examples include a methoxymethyl group, a methoxyethyl group, and an ethoxyethyl group. The hydroxyalkyl group represented by X ₁ and X ₂ preferably has 1 to 5 carbon atoms, and more preferably a hydroxyethyl group. Preferred X ₁ and X ₂ are a hydrogen atom, a methyl group, an ethyl group, a hydroxyethyl group, a methoxymethyl group, a methoxyethyl group and an ethoxyethyl group, more preferably a hydrogen atom and a methyl group, and most preferably It is a hydrogen atom.

Preferred cations represented by M ¹ , M ² , M ³ and M ⁴ may be the same or different in the molecule, and the onium group may be, for example, an ammonium group (eg, ammonium group, tetraethylammonium group). Examples of the group) and alkali metal atoms include metal atoms such as lithium, sodium and potassium), and examples of the alkaline earth metal atoms include metal atoms such as calcium, magnesium and barium, and pyridinium. More preferably, it is an alkali metal atom.

Of the integers 0 to 5 represented by t and u,
It is preferably 0 or 1, and more preferably 0. When t and u are 2 or more, a plurality of R ₂ may be the same or different, and a plurality of R ₆ are the same.

Since the compound of the general formula (II) has two asymmetric carbons, it has three isomers of SS isomer, SR isomer and RR isomer. SS form and SR form are preferable, and SS is more preferable.
It is the body. However, since it may be racemized during the synthesis of the ligand, the passage of time, and the preparation of the solution, the SS form may slightly contain the SR form or the RR form. The optical purity of the SS body is preferably 90% ee, more preferably 95% ee.
e or more, and more preferably 99% ee or more.
Specific examples of the compound represented by the general formula (II) described above are shown below, but the invention is not limited thereto.

[0046]

[Chemical 10]

[0047]

[Chemical 11]

[0048]

[Chemical 12]

[0049]

[Chemical 13]

Among the above specific examples, particularly preferred compounds are (II-3), (II-10), (II-11) and (II-1).
6).

The compound represented by the general formula (II) is a chelate chemistry (5) edited by Keihei Ueno, Nankodo page 311 (synthesis of ethylenediamine-N, N'-disuccinic acid), Inorgnic C
hemistry, 7,2405 (1968), Chm.Zvesti., 20,414 (1966), Z
hurnal Obshchei Khinii, 49,659 (1978) and others WO95 /
12570, WO96 / 01802, WO96 / 01803, WO96 / 01804, WO96 / 35
662, US5466867, EP0694528, EP0731171, WO96 / 32371,
It can also be synthesized by referring to the method described in each publication such as GB2299809, WO96 / 35662, DE19518150 and the like.

In the general formula (III), R ₃₁ , R ₃₂ , R
₃₃ may be the same or different, and each of them may be a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 6 carbon atoms, a carboxyalkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Hydroxyalkyl group with 1 to 1 carbon atoms
Represents the carboxyalkylaminoalkyl group of 6.
Moreover, the total sum of the carboxyl groups contained in R ₃₁ , R ₃₂ and R ₃₃ is 2 or more. Preferred alkyl groups are methyl group, ethyl group, i-propyl group and n-propyl group, preferred alkoxyalkyl groups are methoxyethyl group and ethoxyethyl group, and preferred hydroxyalkyl groups are hydroxymethyl group and hydroxy group. Ethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, preferred carboxyalkyl group is carboxymethyl group, preferred carboxyalkylaminoalkyl group is carboxymethylaminoethyl group and dicarboxymethylaminoethyl group. is there.

Specific examples of the compound represented by the general formula (III) are shown below, but the invention is not limited thereto. Diethylenetriamine pentaacetic acid iminodiacetic acid methyliminodiacetic acid N- (2-acetamido) iminodiacetic acid nitrilotriacetic acid N- (2-carboxyethyl) iminodiacetic acid N-hydroxyethyliminodiacetic acid

Particularly preferred compounds among the specific examples are diethylenetriaminepentaacetic acid, methyliminodiacetic acid and nitrilotriacetic acid. Many of the compounds represented by the general formula (III) are commercially available, and the above-mentioned chelate chemistry (5) edited by Keihei Ueno, Nankodo page 311 (synthesis of ethylenediamine-N, N'-disuccinic acid), Inorgnic Chemist
Ry, Volume 7, page 2405 (1968) and the like.

Iron (II) used in the bleaching solution in the present invention
The complex salt of I) may be a complex-forming compound of the general formula (I), (II) or (III) and an iron (III) compound (for example, iron (III) oxide, ferric sulfate, ferric chloride, bromide). Ferric acid, iron (III) nitrate, etc.) may be added and dissolved as a complexed iron complex salt by reacting with ferric nitrate, and the complex forming compound and iron (III) salt (for example, ferric sulfate) , Ferric chloride, ferric bromide, iron (III) nitrate etc.)
It is also possible to add and to the bleaching solution to form a complex in the bleaching solution to obtain an iron complex salt aqueous solution. When the complex salt formation is carried out in the bleaching solution, the complex-forming compound may be slightly in excess of the amount required for complex formation of iron (III) ions, and when added in excess, it is usually 0.01 to 20%. It is preferable to make it excessive in the range.

The above general formulas (I), (II) and (II)
The iron (III) complex of aminopolycarboxylic acid represented by I) may be used in combination of two or more, if necessary. The amount of the aminopolycarboxylic acid iron (III) complex added is 0.1 mol to 2.0 mol, preferably 0.15 mol to 1.5 mol, per liter of the treatment liquid.

The processing solution having a bleaching ability according to the present invention includes
If desired, a free aminopolycarboxylic acid salt which is not chelated with the iron (III) salt may be added. The preferable addition amount is 0.001 mol to 1 mol / liter, preferably 0.005 mol to 0.1 mol / liter.

The processing solution having a bleaching ability of the present invention preferably contains at least one compound represented by the following general formula (A) for the purpose of preventing the formation of precipitates, desilvering and improving the color recovery property. . Next, the compound represented by formula (A) will be described in detail. Formula _{(A): A 5 (-COOM} 5) n 6 in formula (A), A ₅ represents a n _6-valent organic radical, n
₆ represents an integer of 1 to 3. When n ₆ = 1, A ₅ represents an alkyl group or a phenyl group, when n ₆ = 2, A ₅ represents a single bond or a divalent linking group, and when n ₆ = 3, A ₅ represents a trivalent organic group. Represents a group. M ⁵ is a hydrogen atom, an ammonium group,
Organic ammonium group, alkali metal atom (sodium,
Potassium, lithium, etc.).

The alkyl group represented by A when n ₆ = 1 preferably has 1 to 10 carbon atoms, and more preferably 2 to 5 carbon atoms. Examples of the substituent of the alkyl group and the phenyl group include a hydroxy group, a halogen atom, an amino group, a sulfo group and an acylamino group, and a hydroxy group is particularly preferable.

When n ₆ = 2, A is specifically a substitution,
It represents an unsubstituted alkylene group, alkenylene group, phenylene group, cyclohexylene group, divalent heterocyclic group and the like. n
_{When 6} = 3, A represents a trivalent linking group, specifically, 3
A valent benzene ring group, a trivalent alicyclic 6-membered ring group, a trivalent heterocyclic group and the like. Specific examples are shown below, but the present invention is not limited thereto.

[0061]

[Chemical 14]

[0062]

[Chemical 15]

[0063]

[Chemical 16]

[0064]

[Chemical 17]

Among the above compounds, in the present invention, n = 2
Dicarboxylic acids of are preferred. Specifically, A-20, A-
21, A-22, A-23, A-24, A-26, A-2
7, A-28, A-29 can be mentioned. The addition amount of these organic acids is 0.005 to 2.0 mol, preferably 0.05 mol to 1 liter of a bleaching bath.
Contains 1.5 mol. Moreover, you may use together 2 or more types as needed.

The pH of the processing solution having bleaching ability of the present invention is preferably 5-8. In the case of a bleach-fixing solution, it is preferable to separate the bleaching agent-containing part and the fixing agent-containing part from the standpoint of improving stability during storage. Various bleaching accelerators can be added to the processing solution having bleaching ability of the present invention.

Examples of such a bleaching accelerator include, for example, US Pat. No. 3,893,858, German Patent 1,290,812 and British Patent 1,138,842.
No. 5, JP-A-53-95630, Research Disclosure No. 17129 (July, 1978), compounds having a mercapto group or a disulfide group, thiazolidine derivatives described in JP-A No. 50-140129, U.S. Pat. Thiourea derivatives described in JP-A-3,706,561, iodides described in JP-A-58-16235, polyethylene oxides described in German Patent No. 2,748,430, and JP-B-45-8836. The polyamine compound described in 1) and the like can be used. Particularly preferred are the mercapto compounds described in British Patent No. 1,138,842.

In addition to the bleaching agent and the above-mentioned compounds, the treatment liquid having a bleaching ability constituting the present invention includes bromide such as potassium bromide, sodium bromide, ammonium bromide, or chloride such as potassium chloride and chloride. Rehalogenating agents such as sodium, ammonium chloride and the like can be included. The concentration of the rehalogenating agent is 0.1 to 5 mol, preferably 0.5 to 3 mol, per liter of the processing solution having a bleaching ability.

As the metal corrosion inhibitor, it is preferable to use an alkali metal nitrate or ammonium nitrate, especially ammonium nitrate. As the fixing agent used in the bleach-fixing solution according to the present invention and the fixing solution optionally used, thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate and potassium thiosulfate, sodium thiocyanate, ammonium thiocyanate, Thiocyanates such as potassium thiocyanate, thiourea, thioether and the like can be used. Of these, it is most preferable to use ammonium thiosulfate.

The amount of the fixing agent is 0.3 to 3 mol, preferably 0.5 to 2 mol, per liter of the bleach-fixing solution or the fixing solution. From the viewpoint of accelerating fixing, ammonium thiocyanate (rhodanammonium), thiourea and thioether (for example, 3,6-dithia-1,8-octanediol) can be used in combination, and the amount of these compounds used in combination is also possible. Is 0.0 per liter of fixer or bleach-fixer
The amount is generally 1 mol to 0.1 mol, but depending on the case, the fixing promoting effect can be significantly enhanced by using 1 to 3 mol.

The fixing solution or the bleach-fixing solution contains a sulfite such as sodium sulfite or potassium sulfite as a preservative.
Ammonium sulfite and hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds such as acetaldehyde sodium bisulfite and the like can be included. Further, various fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol can be contained, and particularly as a preservative, sulfin described in JP-A-62-143048. It is also preferable to use an acid compound.

In the present invention, the bleach-fixing solution (mother liquor) is
At the start of processing, a bleaching solution and a fixing solution, which are separately prepared, may be mixed in appropriate amounts, or the compound used in the bleach-fixing solution may be dissolved in water. Regarding the replenishing amount of the fixing solution, the bleach-fixing solution, the processing time, etc., JP-A-3-
It is described in detail in pages 6 to 8 of JP 150563.

Details of the color developing solution used in the present invention are described in JP-A-3-150563, pp. 8-11.
Page. The processing method of the present invention can also be used for color reversal processing. As the black and white developer used at this time,
It is called a black-and-white first developing solution which is used for reversal processing of a commonly known color light-sensitive material. Various well-known additives which are well-known and used in addition to the black-and-white developing solution used in the processing solution of the black-and-white silver halide light-sensitive material can be contained in the black-and-white developing solution of the color reversal photographic material. Details are described in JP-A-3-150563.

The processing method according to the present invention comprises the above-mentioned processing steps such as color development, bleaching, bleach-fixing and fixing. Here, after the bleach-fixing or fixing step, treatment steps such as washing and stabilizing are generally carried out, but after the bath having fixing ability, the stabilizing treatment is carried out without substantially washing with water. A simple treatment method to be performed can also be used.
Details of these steps are described in JP-A-3-150563.

Next, the container constituting the photographic processing agent according to the present invention will be described in detail. The present invention is characterized in that the container used for filling the processing agent composition is made of polylactic acid or cellulose acetate, whereby the photographic processing agent composition having a bleaching ability is stable for a long period of time. Saved. Polylactic acid is thermoplastic and can be made by molding the container body by heating and melting. Cellulose acetate can be dissolved in a mixed solvent of acetone and methylene chloride to form a dope, which can be molded to obtain a container body.

Polylactic acid is a trade name such as Ecopla (Cargill Japan Co., Cargill Dow Polymers Co., Ltd.), Lakurey (Shimadzu Corporation), Reishia (Mitsui Chemicals, Inc.), and cellulose acetate is CellGreen PCA ( Daicel Chemical Industry Co., Ltd., Proupura (Environmental Chemistry Co., Ltd.)
All of them are commercially available under the trade names such as, and the containers can be obtained by consigning the plastic bottle manufacturers in the city.

A heat-resistant stabilizer, a weather-resistant stabilizer, a modifier, a lubricant, a coloring agent, a filler and the like may be added to the container material of polylactic acid or cellulose acetate within a range not impairing the object of the present invention. it can. To these compounding components, pigments such as carbon black, titanium white, calcium silicate, and silica that do not adversely affect the alkaline developing composition, calcium carbonate, and 2,6-di-t-butyl-4-methylphenol (BHT) are added. Agents, dicetyl sulfide, tris (laurylthio) phosphite, other known antioxidants such as amine-based, thioether-based, phenol-based, and slip agents such as stearic acid or metal salts thereof, 2
Examples include known ultraviolet absorbers that are compatible with polylactic acid or cellulose acetate such as hydroxy-4-n-octyloxybenzophenone, and known plasticizers that are compatible with polylactic acid or cellulose acetate. The total amount of these ingredients is 50% of the total amount of the mixture of container materials.
The following is desirable. Preferably, the proportion of polylactic acid or cellulose acetate is 85% or more and does not contain a plasticizer, and more preferably the proportion of polylactic acid or cellulose acetate is 95% or more and does not contain a plasticizer.

The container used in the present invention preferably has a container body having a certain degree of flexibility and impact absorption and a hard mouth portion protruding from the container body. Further, in order to enclose the photographic processing composition, the mouth portion is configured such that the upper opening is opened and closed by attaching and detaching a cap (lid member) screwed onto the mouth portion. The container according to the present invention may have any shape as long as it is made of the above-mentioned material,
For example, a rectangular container that has been conventionally used (see FIG. 1).
(See FIG. 2) or a round container (see FIG. 2). Other than that, for example, Japanese Patent Laid-Open No. 2000-2973 and 2
It also includes a container (see FIG. 3) in a use form in which it is mounted on the automatic processor disclosed in each publication of 000-3014 and is automatically opened to automatically adjust the liquid. In addition, a storage box made of cardboard, corrugated cardboard or paper, tex made by compression molding of fiber waste, wood waste, etc. with a rectangular or square cross section perpendicular to the vertical axis (height) direction as a material The present invention can also be applied to a plastic container of a so-called cubiter that is housed and protected in a case.

The container can be manufactured from either polylactic acid or cellulose acetate by heat-melting or by dissolving it in a solvent and doping it, followed by blow molding or injection blow molding. Also, the cap can be made of any material by injection molding.

A typical example of the processing agent container designed so that it can be attached to the above-mentioned automatic processor will be described with reference to FIG. 3. A port portion 1300 for letting out the processing agent composition and the port portion are closed. A lid 1310 and a seal member (combination of 1308 and 1316), a bottom portion provided on the side facing the mouth portion, and a columnar portion 1302 sandwiched between the mouth portion and the bottom portion and substantially containing the treatment agent composition, A container for a photographic processing composition comprising a shoulder portion 1304 connecting a columnar portion and a mouth portion, wherein the projection surface onto the bottom surface of the columnar portion has a long side of 40 to 100 mm in many cases. And the ratio of the short side to the long side is a rectangle or a square with a ratio of 0.7 to 1.0, or the inner diameter is often 40 to 100 mm, and the ratio of the height of the columnar portion to the long side or the inner diameter is , 2.0 to 4.0 times, columnar shoulder Angle from the bottom to the mouth (angle with the bottom) is 15 to 45 °, and the density is 1.25.
Polylactic acid as a single constituent resin, which is mounted in an automatic processor with the mouth down while being filled with the photographic processing composition, and the photographic processing composition in the container Is discharged to the replenisher tank, and the inside of the empty container is washed.

The mouth portion 1300 is formed in a substantially cylindrical shape, and a circular or square flange portion is provided at the boundary with the shoulder portion 1304 for stabilizing the fixing to the developing device mounting portion. Is also preferable. The mouth portion 1300 is integrally formed with the container main body columnar portion 1302 by blow molding or injection blow molding. At this time, the mouth portion 130 is formed.
The 0 portion can be formed to be thicker than the container body 12 because it has a smaller diameter than the container body columnar portion 1302, and thus the mouth portion 1300 is formed to be hard to some extent. Here, the average thickness of the mouth portion 1300 and the mouth portion including the vicinity thereof is preferably 0.5 to 4
mm, more preferably 0.5 to 3 mm, particularly preferably 1.2 mm to 2.5 mm, and the average thickness of the container body 12 is preferably 0.1 mm to 1.5 m.
m, more preferably 0.2 mm to 0.7 mm, particularly preferably 0.3 mm to 0.5 mm,
The difference between the two is preferably 0.2 mm, more preferably 0.
It is set to about 5 mm. Further, the ratio of the average wall thickness of the mouth portion to the average wall thickness of the main body portion is preferably about 2.0 to 10.0. By doing so, the total weight can be reduced without impairing usability.

A male screw portion 1306 is formed on the outer periphery of the upper end portion of the mouth portion 1300.
A cap 1310 as a hard lid member having an internal thread portion that is screwed to 6 is formed on the inner wall thereof is screwed to the mouth portion 130.
The upper opening of 0 is designed to be opened and closed. The cap 1310 is preferably formed by molding polylactic acid, but another plastic material such as polypropylene or high density polyethylene (HDPE) is used in order to improve the screwability (liquor property) with the mouth portion 1300 of the container body. You may form by. As the high-density polyethylene, for example, one having a density larger than 0.940 g / cc, preferably 0.9
It is possible to use one having a value of more than 40 g / cc and 0.98 g / cc or less.

Although the shape of the container which can be mounted on the minilab developing machine with the automatic opening and automatic liquid preparation has been described above with reference to FIG. 3, the conventional general-purpose containers shown in FIGS. 1 and 2 are also capped. With the exception of the fact that 1310 is not a tubular shape but a sealing shape, the sealing members 1308 and 1316 are not necessary, and that the size of each member can be selected wider than the above according to the purpose, what is described in FIG. , Substantially applies.

The oxygen permeability of the container is at least 0.00
5 ml / m ² · s · MP (20 ° C., 65% RH), preferably 0.01 ml / m ² · s · MP (20 ° C.,
65% RH), more preferably 0.1 ml / m ² · s
-MP (20 ° C., 65% RH) or higher is preferable, and the upper limit thereof is determined within a range permitted by constraints such as strength, handleability and moisture permeability of the container. However, in the present invention, it is not a necessary condition that the container material itself has high oxygen permeability, and the average oxygen permeation rate over the entire area of the vessel wall determined by the strength, shape, moldability, crystallinity of the container is high. It is necessary.

Although FIGS. 1, 2 and 3 exemplify the case where the cross-sectional shape of the container body orthogonal to the axis is circular or rectangular, the present invention is not limited to this, and the cross-section of the container body is not limited to this. The shape may be, for example, an elliptical shape. In this way, when the cross-sectional shape of the container body is elliptical, it becomes possible to fill a larger volume of liquid than a circular container with the same height dimension and the short radius of the ellipse being the same as its diameter. Further, even a container having a considerably large capacity (for example, 2 liter to 5 liter) can be grasped by hand. In the case of photographic processing solutions, it is often the case that several types of containers are combined and stored in one box at the same time. The container has less dead space and can be packed efficiently.

The cross section of the container body perpendicular to the axis has a quadrangular shape,
The shape may be polygonal such as rectangular, hexagonal, or octagonal, or elliptical. In particular, when the cross-sectional shape orthogonal to the axis is hexagonal, in the case of packing a large number of boxes, the so-called By arranging them in a honeycomb shape, it is possible to pack them more efficiently.

The processing to which the present invention is applied is used for processing any general-purpose silver halide color light-sensitive material. The layer structure, film thickness and silver halide emulsion of the silver halide color light-sensitive material are described in JP-A-3-150563, No. 11
It is specifically described on pages 14 to 14. Photographic additives that can be used in color light-sensitive materials are also described in RD, and the relevant portions are shown in the table below.

[0088]   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, pages 866 to 868     Supersensitizer ~ 649, right column 4. Whitening agent page 24 page 647 page right column page 868 5. Light absorber, pages 25 to 26, page 649, right column, page 873     Filter ~ 650 page left column     Dye, ultraviolet     Line absorber 6. Binder 26 pages 651 pages left 873 to 874 pages 7. Plasticizer, page 27, page 650, right column, page 876     lubricant 8. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876     Surfactant 9. Static 27 pages 650 pages right column 876-877 pages         Preventive agent Ten. Matting agent pp. 878-879

Regarding various couplers and solvents,
It is specifically described in JP-A-3-150563 and the patents cited therein.

[0090]

[Example 1]

<Containers> Using the following plastic raw materials, processing composition containers D and E according to the present invention and comparative containers A, B and C were produced by injection blow molding. Each container is composed of a columnar portion, a mouth and a cap having the shape shown in FIG. 1. The screwing state of the cap and the mouth is in accordance with the description of FIG. 3, but the cap is the same as that of FIG. A sealing cap that covers the container and is sealed. The internal volume is 1.2 liters, and the wall thickness of each columnar portion is 1 mm.

[0091] Container fee Remarks A PET Comparative Example B PVC Comparative example C LDPE Comparative Example D Polylactic acid The present invention E Cellulose acetate The present invention

<Photosensitive material for test and exposure> The following commercially available 3
A 5 mm color negative film was used. KODAK GOLD1600 # 2228318 FUJUFIKM SUPERIA1600 # P03
102 Using the standard light source for sensitometry and neutral light wedge defined in the international standard (ISO5800) to the above film, 1
An exposure of 0 CMS was performed and the following processing was performed.

<Treatment> The treatment process and the composition of the treatment liquid are shown below.

The rinse liquid is a countercurrent system of (2) → (1), and the fixing liquid is also connected from (2) to (1) by a countercurrent pipe. In addition, 15 ml of a replenishing amount of the stabilizing solution is added to the fixing solution (2). The amount of the developing solution brought into the bleaching step, the amount of the bleaching solution brought into the fixing step, and the amount of the fixing solution brought into the washing step were all in the light-sensitive material 35.
It was 2.0 ml per mm width 1.1 m. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Tank liquid     Diethylenetriamine pentaacetic acid 2.0 g     Sodium 4,5-dihydroxybenzene-1,3-disulfonate                                           0.4 g     Disodium-N, N-bis (sulfonate ethyl) hydroxylamine                                         10.0 g     Sodium sulfite 4.0 g     1.4 g of potassium bromide     4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl)       Aniline sulfate 4.7g     39 g potassium carbonate     Diethylene glycol 10.0g     Ethylene urea 3.0g     Hydroxylamine sulfate 2.0g     1.0L with water added     pH (adjusted with sulfuric acid and KOH) 10.07

[0096] (Bleaching solution) Tank solution     1,3-Diaminopropanetetraacetic acid ferric ammonium monohydrate                                           120 g     Ammonium bromide 50g     Succinic acid 30g     Maleic acid 40g     Imidazole 20g     1.0L with water added     pH (adjusted with ammonia water and nitric acid) 4.6

[0097] (Fixing liquid) Tank liquid     Ammonium thiosulfate (750 g / L) 280 ml     20 g of ammonium bisulfite aqueous solution (72%)     Imidazole 5g     1-mercapto-2- (N, N-dimethylaminoethyl)       Tetrazole 1g     Ethylenediaminetetraacetic acid 8g     Add water 1L     pH (adjusted with ammonia water and nitric acid) 7.0

(Stabilizing Solution) Tank Solution Formalin (37%) 1.2 mL Surfactant C ₁₀ H ₂₂ O (CH ₂ CH ₂ O) ₁₀ H) 0.4 g Ethylene glycol 1.0 g Water was added to 1.0 L pH

<Stability Test with Time and Results> Each bleaching solution is
Fill each container A to E with 1 liter each, 40
The one that had been stored at 0 ° C for 2 months was used. The liquid after the passage of time was visually observed for the presence of precipitate. The concentration of each sample treated with each bleaching solution was measured, and the residual silver amount, which is a measure of desilvering property, was determined by fluorescent X-ray for each maximum concentration part. The results are shown in Table 1. In Table 1, the "no aging" level is a standard for comparison, which was used in a fresh solution without filling the container with the prepared bleaching solution and without allowing it to age.

[0100]

[Table 1]

In Table 1, when the containers D and E according to the present invention were used, excellent performance equivalent to that of the standard bleaching solution for comparison marked as "no aging" was maintained.
In the case of using the containers A, B and C using the materials of the comparative example, a precipitate (decomposition product) was generated over time, and the bleaching ability was significantly reduced due to an increase in the amount of the divalent iron compound. It is shown that silver failure (increased residual silver amount) occurred.

Example 2 (1) Sample of silver halide color photographic light-sensitive material (00
Preparation of 1) (Preparation of emulsion A) 1.06 liters of deionized distilled water containing 5.7% by weight of deionized gelatin was added with 10 parts of NaCl.
% Solution of 46.3 ml, H ₂ SO ₄ (1N) of 46.4 ml, and compound A of 0.012 g.
When the liquid temperature was adjusted to 50 ° C after the addition, 0.1 mol of silver nitrate and NaCl were immediately added while performing high-speed stirring.
0.1 mol was added into the reaction vessel over 10 minutes. Subsequently, 1.5 mol of silver nitrate and NaCl solution were added over 60 minutes by a flow rate acceleration method so that the final addition rate was 4 times the initial addition rate. Next, 0.2 mol% silver nitrate and NaCl solution were added at a constant addition rate over 6 minutes. At this time, K ₃ IrCl was added to the NaCl solution.
₅ (H ₂ O) was added in an amount of 5 × 10 ⁻⁷ mol based on the total amount of silver to dope the particles with iridium.

Further, 0.2 mol of silver nitrate, 0.16 mol of NaCl and 0.04 mol of KBr solution were added over 6 minutes. At this time, K ₄ Ru (CN) ₆ corresponding to 1 × 10 ⁻⁵ mol based on the total amount of silver was dissolved in the aqueous halogen solution and added to the silver halide grains. In addition, during the grain growth in this final stage, an aqueous KI solution corresponding to 0.002 mol based on the total silver amount was added into the reaction vessel over 1 minute. The timing of starting the addition was started when 93% of all particle formation was completed. Thereafter, a precipitating agent for compound B was added at 40 ° C to adjust the pH to around 3.5, and desalting and washing with water were performed.

Deionized gelatin, an aqueous solution of NaCl, and an aqueous solution of NaOH were added to the emulsion after desalting and washing at 50 ° C.
The temperature was raised to pAg 7.6 and pH was adjusted to 5.6. In this way, 97.8 mol% of silver chloride, 2 mol% of silver bromide,
Emulsion containing silver halide cubic grains having a halogen composition of 0.2 mol% of silver iodide and having an average side length of 0.41 μm and a side length variation coefficient of 8% (small size emulsion of emulsion A, large size emulsion and others. The emulsion of the layer was also prepared according to this. While maintaining the emulsion grains at 50 ° C., spectral sensitizing dyes-1 and 2 were added at 3 × 10 ^-4 mol / Ag mol and 3 × 10 ^-5 mol / Ag mol, respectively. Further, 1 × 10 ⁻⁵ mol / Ag mol of thiosulfonic acid compound-1 was added, and a fine grain emulsion doped with iridium hexachloride was added with 90 mol% of silver bromide and 10 mol% of silver chloride having an average particle diameter of 0.05 μm. do it,
Aged for 15 minutes. The fine particles dissolved, which increased the silver bromide content of the host cubic particles to 2.7 mol%. Further, iridium hexachloride was doped at 1 × 10 ⁻⁷ mol / Ag mol. Continuously, sodium thiosulfate 1 x 1
0 ⁻⁵ mol / Ag mol and 2 × 10 ⁻⁵ mol of gold sensitizer-1 were added. Immediately, the temperature was raised to 60 ° C, and then 4
It was aged for 0 minutes and then cooled to 50 ° C. Immediately after the temperature was dropped, mercapto compounds-1 and 2 were added so that the amount of each was 6 × 10 ^-4 mol / Ag mol. Then, after aging for 10 minutes, an aqueous KBr solution was added so as to be 0.008 mol with respect to silver, and after aging for 10 minutes, the temperature was lowered and stored.

[0105]

[Chemical 18]

[0106]

[Chemical 19]

Corona discharge treatment was applied to the surface of a support obtained by coating both sides of paper with a polyethylene resin, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. Samples (001) of a silver halide color photographic light-sensitive material having the layer structure shown below were prepared by sequentially coating the above photographic constituent layers. The coating liquid for each photographic constituent layer was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY) 57 g, color image stabilizer (Cp
d-1) 7 g, color image stabilizer (Cpd-2) 4 g, color image stabilizer (Cpd-3) 7 g, color image stabilizer (Cpd-8) 2
21 g of solvent (Solv-1) and 80 m of ethyl acetate
22 g of a 23.5% by mass gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate.
Emulsified and dispersed in 0 g by a high-speed stirring emulsifying machine (dissolver), and water was added to prepare 900 g of emulsified dispersion A. On the other hand, the emulsified dispersion A and the emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the composition described below. The emulsion coating amount indicates a coating amount equivalent to silver.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used as a gelatin hardening agent for each layer. Also, Ab-1, Ab-2, Ab-3 and A are provided in each layer.
b-4 has a total amount of 15.0 mg / m ² and 60.0, respectively.
It was added so as to be mg / m ² , 5.0 mg / m ² and 10.0 mg / m ² .

[0110]

[Chemical 20]

The silver chlorobromide emulsions of the green and red sensitive emulsion layers include
The following spectral sensitizing dyes were used respectively. Green sensitive emulsion layer

[0112]

[Chemical 21]

(The sensitizing dye D was added per mol of silver halide:
3.0 x 10 for large emulsions ^-FourMole, small size
3.6 × 10 for emulsions^-FourMolar and sensitizing dye E
Per mole of silver halide for large size emulsions
4.0 x 10^-Five7.0 × for moles, small size emulsions
10^-Five1 mole of sensitizing dye F to 1 mole of silver halide
2.0 × 10 for large emulsions^-FourMole, small
2.8 × 10 for Izu emulsion^-FourMol added. ) Red-sensitive emulsion layer

[0114]

[Chemical formula 22]

(The sensitizing dyes G and H are respectively
8.0 x 1 for large emulsions per mol of silver halide
0^-Five10.7 × 10 for moles and small size emulsions^-FiveMo
Added. ) Furthermore, the following compound I was added to the silver halide 1 in the red-sensitive emulsion layer.
3.0 x 10 per mole ^-3Mol added.

[0116]

[Chemical formula 23]

Further, 1- (3-methylureidophenyl) -5-mercaptodetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer at 3.3% per mol of silver halide. × 10 ^-4 mol, 1.0 × 10 ^-3
Mol and 5.9 x 10 ^-4 mol. Furthermore, the second layer, the fourth layer, the sixth layer and the seventh layer each have a thickness of 0.2 m.
g / m ² , 0.2 mg / m ² , 0.6 mg / m ² , 0.1
It was added so as to be mg / m ² . Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mol per mol of silver halide, respectively. 2 x 10 ^-4
Mol added. In addition, a copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1,
Average molecular weight 200000-400000) 0.05 g
/ M ^{2 was} added. Further, the second layer was added fourth layer and the sixth layer in disodium catechol-3,5-disulfonate as respectively a ^{6mg / m 2, 6mg / m} 2, 18mg / m 2. Also, to prevent irradiation,
The following dyes (the amount in parentheses represents the coating amount) were added.

[0118]

[Chemical formula 24]

(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). Silver halide emulsion,
Indicates the coating amount in terms of silver. Support polyethylene resin laminated paper [white pigment (TiO ₂ ; polyethylene resin on the first layer side;
Content 16% by mass, ZnO; content 4% by mass) and optical brightener (4,4'-bis (5-methylbenzoxazolyl) stilbene: content 0.03% by mass), bluish dye ( Including ultramarine)

[0120] First layer (blue sensitive emulsion layer)   Emulsion A (Large size emulsion with average grain size 0.7 μm and average grain size 0.4 1: 1 mixture with a small size emulsion of μm (silver molar ratio). Coefficients of variation of particle size are 0.10 and 0.08. Each service (Equivalent to Izu emulsion except for grain size) 0.24   Gelatin 1.25   Yellow coupler (ExY) 0.57   Color image stabilizer (Cpd-1) 0.07   Color image stabilizer (Cpd-2) 0.04   Color image stabilizer (Cpd-3) 0.07   Color image stabilizer (CPd-8) 0.02   Solvent (Solv-1) 0.21

[0121] Second layer (color mixing prevention layer)   Gelatin 0.99   Color mixing inhibitor (Cpd-4) 0.09   Color image stabilizer (Cpd-5) 0.018   Color image stabilizer (Cpd-6) 0.13   Color image stabilizer (Cpd-7) 0.01   Solvent (So1v-1) 0.06   Solvent (So1v-2) 0.22

[0122] Third layer (green sensitive emulsion layer)   Silver chlorobromide emulsion B (gold sulfur sensitized cube, large with an average grain size of 0.45 μm 1: 3 mixture of size emulsion and small size emulsion of 0.35 μm (silver molar ratio). particle Coefficients of variation of size distribution are 0.10 and 0.08 respectively. Silver iodide for each size emulsion 0.15 mol% is contained in the vicinity of the grain surface, and silver bromide 0.4 mol% is localized on the grain surface. Included) 0.14   Gelatin 1.36   Magenta coupler (ExM) 0.15   Ultraviolet absorber (UV-A) 0.14   Color image stabilizer (Cpd-2) 0.02   Color image stabilizer (Cpd-4) 0.002   Color image stabilizer (Cpd-6) 0.09   Color image stabilizer (Cpd-8) 0.02   Color image stabilizer (Cpd-9) 0.03   Color image stabilizer (Cpd-10) 0.01   Color change stabilizer (Cpd-11) 0.0001   Solvent (Solv-3) 0.11   Solvent (Solv-4) 0.22   Solvent (Solv-5) 0.20

[0123] Fourth layer (color mixing prevention layer)   Gelatin 0.71   Color mixing inhibitor (Cpd-4) 0.06   Color image stabilizer (Cpd-5) 0.013   Color image stabilizer (Cpd-6) 0.10   Color image stabilizer (Cpd-7) 0.007   Solvent (Solv-1) 0.04   Solvent (Solv-2) 0.16

[0124] Fifth layer (red sensitive emulsion layer)   Silver chlorobromide emulsion C (gold sulfur sensitized cube, large with an average grain size of 0.40 μm) 5: 5 mixture of size emulsion and 0.30 μm small size emulsion (silver molar ratio). particle Coefficients of variation of size distribution are 0.09 and 0.11. With any size emulsion Also contains 0.1 mol% of silver iodide near the surface of the grain and 0.8 mol% of silver bromide on the surface of the grain. 0.12)   Gelatin 1.11.   Cyan coupler (ExC-2) 0.13   Cyan coupler (ExC-3) 0.03   Color image stabilizer (Cpd-1) 0.05   Color image stabilizer (Cpd-6) 0.06   Color image stabilizer (Cpd-7) 0.02   Color image stabilizer (Cpd-9) 0.04   Color image stabilizer (Cpd-10) 0.01   Color image stabilizer (Cpd-14) 0.01   Color image stabilizer (Cpd-15) 0.12   Color image stabilizer (Cpd-16) 0.03   Color image stabilizer (Cpd-17) 0.09   Color image stabilizer (Cpd-18) 0.07   Solvent (So1v-5) 0.15   Solvent (So1v-8) 0.05

[0125] Sixth layer (UV absorption layer)   Gelatin 0.46   UV absorber (UV-B) 0.45   Compound (S1-4) 0.0015   Solvent (Solv-7) 0.25 Seventh layer (protective layer)   Gelatin 1.00   Acrylic modified copolymer of polyvinyl alcohol   (Modification degree 17%) 0.04   Liquid paraffin 0.02   Surfactant (Cpd-13) 0.01

[0126]

[Chemical 25]

[0127]

[Chemical formula 26]

[0128]

[Chemical 27]

[0129]

[Chemical 28]

[0130]

[Chemical 29]

[0131]

[Chemical 30]

[0132]

[Chemical 31]

[0133]

[Chemical 32]

[0134]

[Chemical 33]

[0135]

[Chemical 34]

(2) Development Processing The above sample (001) was processed into a 127 mm roll,
Fuji Photo Film Co., Ltd. automatic printer FAP700
Imagewise exposure was performed using 0, and continuous development processing (running processing) was carried out by the following processing steps and processing solutions until the replenishing amount of the color developing solution was twice the developing tank capacity (2 rounds). Each of the bleach-fixing solutions A was prepared in the same manner as in Example 1.
Each of the containers A to E described in 1 above was filled and allowed to stand at 40 ° C. for 2 months before use.

<Development processing> Processing step Temperature time (second) Replenishment amount (mL / m ² ) Color development 38.0 ° C. 45 seconds 45 Bleach fixing 35.0 ° C. 45 seconds A agent 25 + B agent 25 Rinse (1) 33.0 ° C 20 sec-Rinse (2) 33.0 ° C 20 sec-Rinse (3) 33.0 ° C 20 sec-Rinse (4) 33.0 ° C 20 sec 170 Dry 80 ° C 40 sec Note) * Rinse Was a 4-tank countercurrent system of (4) → (3) → (2) → (1). ** The bleach-fix solution was prepared by directly replenishing each of the agents A and B directly into the tank.

The composition of each processing liquid is as follows. [Color developer] Tank solution Replenisher Triethanolamine 2.0g 10.0g Ethylenediaminetetraacetic acid 2.0g 2.0g Tyrone 0.15g 0.5g Potassium chloride 10.0g- Potassium bromide 0.04g 0.01g Sodium sulfite 0.1g 0.2g P-1 (compound below) 1.0 g 2.0 g S-1 (compound below) 1.0 g 2.0 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine                                               5.0 g 10.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-a     Minoaniline ・ 3/2 sulfuric acid ・ monohydrate 5.0g 15.0g Potassium carbonate 26.0g 26.0g   Add water 1000 ml 1000 ml   pH (adjusted with 25 ° C / potassium hydroxide) 10.00 12.50

[0139] [Bleaching fixer, replenisher A]   Ethylenediaminetetraacetic acid iron (III) ammonium 180g   Ethylenediaminetetraacetic acid 2g   30 g of sodium m-carboxysulfinate   Add 1000 ml of water   pH (adjusted with 25 ° C / nitric acid and aqueous ammonia) 6.0

[0140] [Bleaching fixer, replenisher B]   Ethylenediaminetetraacetic acid 2g   Ammonium thiosulfate (750 g / l) 450 ml   Ammonium sulfite 60g   Potassium metabisulfite 80g   Imidazole 50g   Nitric acid (67%) 66 g   Add 1000 ml of water   pH (adjusted with 25 ° C / nitric acid and aqueous ammonia) 6.0   (Note) The bleach-fixing solution tank solution (start solution) is the above-mentioned A agent 250 mL + B agent 25         It was prepared with 0 mL + 500 mL of water and a total volume of 1 liter.

(Rinse replenisher, tank solution) Chlorinated sodium isocyanurate 0.02g Deionized water 1000 ml pH 6.5

[0142]

[Chemical 35]

<Evaluation Test and Results> At the end of the running test, the color paper was exposed using a standard light source for sensitometry and a neutral light wedge, and processed according to the above processing recipe. The amount of residual silver in the maximum density portion of the treated sample was determined by fluorescent X-ray analysis and used as a measure of desilvering property. The processed light-sensitive material was re-bleached with CN-16X.N2 solution (commercially available bleaching solution for color negative processing), and the cyan density was 2.0. The color development rate (%) was determined and the degree of color restoration failure was evaluated. The results are shown in Table 2.

[0144]

[Table 2]

In Table 2, when the containers D and E according to the present invention were used, the same level of desilvering property and color recovery resistance as the comparative standard bleach-fixing solution described as "no aging" was exhibited. On the other hand, containers A, B and C using the material of the comparative example
It is shown that, in the example of using, the desilvering defect (increased residual silver amount) and the cyan recoloring defect occurred remarkably with the passage of time in the container filled state.

[0146]

INDUSTRIAL APPLICABILITY The photographic processing agent of the present invention, which is obtained by filling a photographic processing composition containing a bleaching agent in a container made of a plastic whose main component is polylactic acid or cellulose acetate, is used for a long time in a container form. Even in this case, however, the occurrence of precipitation in the container can be suppressed, and the deterioration of the bleaching ability can be prevented. Moreover, the shape of this container is not particularly limited, and may be a practical shape from the viewpoint of container manufacturing and handling.

[Brief description of drawings]

FIG. 1 is a schematic perspective view of a specific example of a container according to the present invention.

FIG. 2 is a schematic perspective view of another specific example of the container according to the present invention.

FIG. 3 is a schematic perspective view of still another specific example of the container according to the present invention.

[Explanation of symbols]

1300 mouth 1302 Column 1304 Shoulder 1306 screw part 1308 Seal member A 1310 lid 1316 Seal member B

Claims (3)

[Claims] 1. A photographic processing agent comprising a photographic processing composition and a container enclosing the photographic processing composition,
A silver halide color photograph characterized in that the container is made of a plastic containing polylactic acid or cellulose acetate as a main component, and the photographic processing composition is a photographic processing composition containing a bleaching agent. Treatment agent. 2. The silver halide color photographic processing agent according to claim 1, wherein the bleaching agent contains at least one kind of aminopolycarboxylic acid iron (III) complex. 3. The silver halide color photographic processing agent according to claim 1, wherein the bleaching agent further contains at least one compound represented by the following general formula (A). Formula ^{_{(A) A 5 (-COOM 5}} ) n 6 ( wherein, A ₅ represents a n ₆ monovalent organic group, A ₅ when .n ₆ = 1 n ₆ is an integer of 1 to 3 When n ₆ = 2, A ₅ represents a single bond or a divalent linking group, when n ₆ = 3, A ₅ represents a trivalent organic group, and M ⁵ represents an ammonium group. , Represents an alkali metal atom or a hydrogen atom.)