JP3030586B2 - Bleaching solution or bleach-fixing solution and processing method of silver halide color photographic light-sensitive material using these processing solutions - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing solution having a bleaching ability for a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having excellent biodegradability and rapid processing. The present invention relates to a bleaching solution for a material, a bleach-fixing solution, and a method for processing a silver halide color photographic light-sensitive material using the same.

[0002]

BACKGROUND OF THE INVENTION Generally, silver halide color photographic light-sensitive materials are processed with a color developing solution, a bleaching solution, a fixing solution, a bleach-fixing solution, a stabilizing solution and the like. Among these processing solutions, bleaching agents for bleaching silver are added to the bleaching solution and the bleach-fixing solution, and are currently most commonly used for color paper processing, color negative film processing, and the like. Is a ferric ethylenediaminetetraacetic acid complex salt. However, ferric ethylenediaminetetraacetic acid complex is not biodegradable (Biodegrada
abilities) are poor, and if spilled into rivers and soil, they would accumulate without being decomposed or would drift for a long time, which is not desirable from the standpoint of global environmental protection. Also,
As a bleaching agent that has recently been used, for example, JP-A-2-03041
, JP-A-2-103040, JP-A-63-250651, ferric salt of 1,3-propanediaminetetraacetic acid (PD
TA / Fe). This PDTA.Fe is a compound having excellent silver bleaching ability, suitable for rapid processing, and excellent in biodegradability, but has drawbacks in practical use. That is, when bleaching is performed immediately after color development, bleaching fog is generated. To solve this problem, a technique of lowering the pH using acetic acid or the like is considered, but in such a case, odor is a problem. turn into.

Another problem with PDTA / Fe is that when it is processed with a fixing solution after a bleaching solution using PDTA / Fe, or when it is used as a bleaching agent for a bleach-fixing solution, it has a strong oxidizing power. The point is that thiosulfate as a fixing agent is decomposed and sulfuration occurs.

[0004] Another bleaching agent is disclosed in JP-A-61-118.
No. 752, JP 61-50145, JP 61-50150, JP 6
A ferric diethylenetriaminepentaacetic acid complex described in, for example, the specification of JP-A-1-50147 is known, but it still has disadvantages.

[0005] Not only is the biodegradability poor, but also when the bleach is treated with color paper, yellow stains occur at the edges. This is particularly noticeable when low replenishment processing is performed, and is a problem that cannot be ignored.

EPO, 430,000A as a bleaching agent with good biodegradability
No. 1 and German Patent No. 3,939,756 are known, but when performing low replenishment processing using these bleaching agents, the desilvering performance deteriorates, and the rapid processing performance deteriorates. It turns out that there are drawbacks that cause problems.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a bleaching solution, a bleach-fixing solution having excellent biodegradability and environmental suitability, and a method for processing a silver halide photosensitive material using these processing solutions. Secondly, the present invention provides a bleaching solution, a bleach-fixing solution, and a method for processing a silver halide color photographic light-sensitive material using these processing solutions, which can provide sufficient processing performance even at low replenishment processing. A third object of the present invention is to provide a bleaching solution and a bleach-fixing solution having excellent rapid processing performance and a method for processing a silver halide color photographic light-sensitive material using these processing solutions.
A fourth object of the present invention is to provide a bleaching solution and a bleach-fixing solution having stable processing performance even at a low processing amount, and a method for processing a silver halide color photographic material using these processing solutions.

[0008] This and other objects will become apparent in the following specification.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have reached the present invention.

(1) The following general formulas [A- II] and [A-II]
At least one ferric complex salt of a compound represented by I, a halogen, characterized by containing a low Do Kutomo one compound represented by the following general formula [B-I] - [B-VII] Bleaching solution or bleach-fixing solution for silver halide color photographic light-sensitive materials.

[0011]

[0012]

[0013]

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Wherein A ₁ , A ₂ , A ₃ and A ₄ are each —CH
₂ OH, represents a -PO ₃ (M) ₂ or -COOM, may each be the same or different. M represents a hydrogen atom, an alkali metal atom or another cation. X is an alkylene group of a substituted or unsubstituted 2-6 carbon atoms _{- (B 1 O) n-} B 2 -
Represents n represents an integer of 1 to 8; B ₁ and B ₂ may be the same or different;
5 represents a substituted or unsubstituted alkylene group. ]

[0015]

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Wherein A ₁ , A ₂ , A ₃ and A ₄ are each —CH
₂ OH, —PO ₃ (M ² ) ₂ or —COOM ^1, which may be the same or different. M ¹ and M ² represent a hydrogen ion, an alkali metal ion or another cation. X is a linear or branched alkylene group having 2 to 6 carbon atoms, an organic group of a saturated or unsaturated to form a ring, or _{- (B 1 O) n-} B 2 - represents a.
n 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 each represent an integer of 1 or more, and may be the same or different, and at least one is 2 or more. ]

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

[0023] (2) and one Kutomo Do small ferric complex salt of the compound represented by the general formula [A-II], wherein Formula [B
-I] - [B-VII] by containing less Do Kutomo one compound represented characterized by (1) a silver halide color photographic light-sensitive material for bleaching or bleach-fixing solution according.

( 3 ) The above general formulas [ A-II] and [A-II]
At least one ferric complex salt of a compound represented by I, the bleaching solution or bleach-fixing solution containing a small Do Kutomo one of the formula [B-I] - compounds represented by [B-VII] A method for processing a silver halide color photographic light-sensitive material, characterized by using:

[0025] Particularly preferred among these are the (2) Bleaching-fixing solution or the like according.

Hereinafter, the present invention will be described in detail.

[0027]

[0028]

[0029]

[0030]

[0031]

The compound represented by formula (A-II) will be described below.

In the formula, A _{1 to} A ₄ may be the same or different and represent —CH ₂ OH, —PO ₃ (M) ₂ or —COOM. M represents a hydrogen atom, an alkali metal atom (eg, sodium or potassium) or another cation (eg, ammonium, methyl ammonium, trimethyl ammonium, etc.). X is an alkylene group of a substituted or unsubstituted 2-6 carbon atoms _{- (B 1 O) n-} B 2 - represents a. B ₁ and B ₂ may be the same or different and each represents a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms.
Examples of the alkylene group represented by X include ethylene, trimethylene, tetramethylene and the like. Examples of the alkylene group represented by B ₁ and B ₂ include methylene, ethylene, trimethylene and the like. The substituent of the alkylene group represented by X, B ₁ or B ₂ includes a hydroxyl group,
And 3 alkyl groups (for example, a methyl group, an ethyl group, etc.). n represents an integer of 1 to 8, preferably 1
~ 4. Preferred specific examples of the compound represented by the general formula [A-II] are shown below, but it should not be construed that the invention is limited thereto.

[0034]

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[0035]

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The compound represented by the general formula [A-II] can be synthesized by a generally known method.

Among these, particularly preferred compounds are (A-II-1), (A-II-3) and (A-II-14).

The compound represented by formula (A-III) will be described below.

In the formula, 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
Represents M ¹ and M ² represent a hydrogen ion, an alkali metal ion (eg, a sodium ion or a potassium ion) or another cation (eg, an ammonium ion, a methyl ammonium ion, a trimethyl ammonium ion, etc.).

X represents a linear or branched alkylene group having 2 to 6 carbon atoms, a saturated or unsaturated organic group forming a ring, or — (B ₁ O) nB ₂ —. B ₁ and B ₂ may be the same or different and each represent an alkylene group having 1 to 5 carbon atoms (including a substituent). n _{1 to} n ₄ each represent an integer of 1 or more, and 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.
As the alkylene group represented by B ¹ and B ^2, methylene, ethylene and trimethylene. Examples of the substituent of the alkylene group represented by X, B ₁ or B ₂ include a hydroxyl group, an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, and the like). n represents an integer of 1 to 8, and preferably 1 to 4. Particularly preferably, it is 1-2. Preferred specific examples of the compound represented by the general formula [A-III] are shown below, but it should not be construed that the invention is limited thereto.

[0041]

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[0042]

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[0043]

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[0044]

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The above (A-III-16) and (A-III-1)
7), (A-III-18), (A-III-19), (A-III-
20) shall include both cis isomers.

The compound represented by the general formula [A-III] can be synthesized by a generally known method.

Particularly preferred compounds among the specific examples are (A)
-III-1), (A-III-2) and (A-III-6).

The amount of the ferric complex salt of the compound represented by the general formulas [A- II ] and [A-III] is preferably 0.1 to 2.0 mol per liter of the bleaching solution or the bleach-fixing solution. , More preferably in the range of 0.15 to 1.5 mol.

In the present invention, the bleaching solution or the bleach-fixing solution is used as a bleaching agent in the general formulas [A- II ] and [A-III].
In addition to the iron complex salt of the compound represented by the formula (II), a ferric complex salt of the following compound can be used.

[A'-1] ethylenediaminetetraacetic acid [A'-2] trans-1,2-cyclohexanediaminetetraacetic acid [A'-3] dihydroxyethylglycine [A'-4] ethylenediaminetetrakismethylenephosphonic acid [A '-5] Nitrilotrismethylene phosphonic acid [A'-6] Diethylenetriamine pentakismethylenephosphonic acid [A'-7] Diethylenetriaminepentaacetic acid [A'-8] Ethylenediamine diorthohydroxyphenylacetic acid [A'-9] Hydroxyethyl Ethylenediaminetriacetic acid [A'-10] Ethylenediaminepropionic acid [A'-11] Ethylenediaminediacetic acid [A'-12] Hydroxyethyliminodiacetic acid [A'-13] Nitrilotriacetic acid [A'-14] Nitrilotripropionic acid [A'-15] triethylenetetramine hexaacetic acid [ '-16] Ethylenediaminetetrapropionic acid [A'-17] 1,3-propylenediaminetetraacetic acid [A'-18] glycol ether diaminetetraacetic acid represented by the aforementioned general formulas [BI] to [B-VII] Specific examples of the compound include (I-1) to (VII-20) described in Japanese Patent Application No. 60-256383, pages 79 to 142. Among the compounds represented by the general formulas [BI] to [B-VII], particularly preferred compounds are (B-1) to (B-30) shown below.

[0051]

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[0052]

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[0053]

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The compounds represented by the general formulas [BI] to [B-VII] are suitably used in an amount of 0.05 g to 50 g, preferably 0.1 g to 20 g, per liter of the processing solution.

Of the above, the most preferred is A
This is a bleach-fix solution using -II.

The temperature of the bleaching solution or the bleach-fixing solution is preferably from 20 to 50 ° C., preferably from 25 to 45 ° C.

The pH of the bleaching solution is preferably 6.0 or less, more preferably 1.0 or more and 5.5 or less. The pH of the bleach-fix solution is preferably 5.0 to 9.0, more preferably 6.0 to 8.5.
It is. The pH of the bleaching solution or the bleach-fixing solution is the pH of the processing tank when processing the silver halide light-sensitive material, and can be clearly distinguished from the pH of a so-called replenisher.

In addition to the above, the bleaching solution or the bleach-fixing solution may contain a halide such as ammonium bromide, potassium bromide or sodium bromide, various fluorescent whitening agents, defoaming agents or surfactants. it can.

A preferable replenishing amount of the bleaching solution or the bleach-fixing solution is 500 ml or less, more preferably 20 ml to 400 ml, most preferably 40 ml to 350 ml, per m ^{2 of the} silver halide color photographic light-sensitive material. , The effect of the present invention becomes more remarkable.

In the present invention, air or oxygen may be blown in the processing bath and in the processing replenisher storage tank, if desired, in order to increase the activity of the bleaching solution or bleach-fixing solution. Agents such as hydrogen peroxide,
Bromates, persulfates and the like may be appropriately added.

As a fixing agent used in the fixing solution or the bleach-fixing solution according to the present invention, thiocyanates and thiosulfates are preferably used. The content of the thiocyanate is preferably at least 0.1 mol / l or more, and more preferably 0.5 mol / l or more, and particularly preferably 1.0 mol / l or more when a color negative film is processed. The thiosulfate content is preferably at least 0.2 mol / l or more, and more preferably 0.5 mol / l or more when a color negative film is processed.

In the present invention, the object of the present invention can be more effectively achieved by using a combination of a thiocyanate and a thiosulfate.

The fixing solution or the bleach-fixing solution according to the present invention may contain, alone or in combination of these fixing agents, pH buffers composed of various salts. Further, it is desirable to contain a large amount of a rehalogenating agent such as an alkali halide or an ammonium halide, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide and the like.

Compounds known to be added to ordinary fixing solutions or bleach-fixing solutions, such as alkylamines and polyethylene oxides, can be added as appropriate.

Incidentally, silver may be recovered from the bleach-fix solution according to the present invention by a known method.

The processing time with the bleaching solution and the fixing solution is optional, but is preferably 3 minutes and 30 seconds or less, more preferably 10 seconds to 2 minutes and 20 seconds, and particularly preferably 20 seconds to 1 minute.
The range is 20 seconds. The processing time with the bleach-fix solution is 4
Minutes or less, and more preferably in the range of 10 seconds to 2 minutes and 20 seconds.

In practicing the present invention, when the ratio of ammonium ions to all cations in the bleaching solution or bleach-fixing solution of the present invention is 50 mol% or less, the effect of the present invention is more excellent. The ratio is more preferably at most 30 mol%, most preferably at most 10 mol%.

In the present invention, it is preferable as an embodiment of the present invention to forcibly agitate the bleaching solution and the bleach-fixing solution. The reason for this is not only that the effects of the object of the present invention can be achieved more favorably, but also from the viewpoint of rapid processing suitability. Here, forcible liquid stirring is not a normal liquid stirring movement,
This means that stirring is performed by adding a stirring means.
As the forced stirring means, the means described in JP-A-64-222259 and JP-A-1-206343 can be employed.

In the present invention, when the crossover time between the color developing tank and the bleaching tank or the bleach-fixing tank is preferably within 10 seconds, more preferably within 7 seconds, bleaching which is an effect different from the present invention is achieved. Effective against fog.

The bleaching solution and the bleach-fixing solution according to the present invention are:
From the viewpoint of the effect of the present invention, it is preferable that acetic acid is not substantially used.

The bleaching solution and the bleach-fixing solution according to the present invention preferably contain a compound represented by the following general formula [II].

In the formula, A represents a valent organic group, n represents an integer of 1 to 6, and M represents an ammonium or an alkali metal (sodium, potassium, lithium, etc.). Or a hydrogen atom.

In the general formula [II], the n-valent organic group represented by A includes an alkylene group (for example, a methylene group,
Ethylene, trimethylene, tetramethylene, etc.),
Alkenylene group (eg ethenylene group etc.), alkynylene group (eg ethinylene group etc.), cycloalkylene group (eg 1,4-cyclohexanediyl group etc.), arylene group (eg o-phenylene group, p-phenylene group etc.), alkane Examples thereof include a triyl group (eg, a 1,2,3-propanetriyl group) and an arenetriyl group (eg, a 1,2,4-benzenetriyl group).

The n-valent group represented by A is a substituent (for example, a hydroxy group, an alkyl group, a halogen atom, etc.)
(E.g., 1,2-dihydroxyethylene, hydroxyethylene, 2-hydroxy-1,2,3-propanetriyl, methyl-p-phenylene, 1-hydroxy-2-chloroethylene, chloromethylene, chloro Ethenylene). Preferred specific examples of the compound represented by the general formula [II] are shown below.

[0075]

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[0076]

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Of the above exemplified compounds, particularly preferred are the exemplified compounds (II-1), (II-3), (II-4) and (II-
5), (II-16) and (II-18), and particularly preferably (II-5).

The compound represented by the general formula [II] is preferably contained in an amount of 0.05 to 2.0 mol per liter of the treatment solution.
More preferably, it is contained in an amount of 0.2 to 1.0 mol.

Next, a color photographic light-sensitive material to which the bleaching solution, the bleach-fixing solution or the processing method of the present invention is applied will be described.

Examples of the light-sensitive material include a color negative film, a color paper and a color reversal. The silver halide grains for a color negative film include an iodine odor having an average silver iodide content of 3 mol% or more. Silver iodide is preferably used, and silver iodobromide containing 4 to 15 mol% of silver iodide is particularly preferred. Among them, the average silver iodide content preferred by the present invention is from 5 mol% to 12 mol%,
Most preferably, it is from 8 mol% to 11 mol%.

In the light-sensitive material for a color negative film used in the present invention, as a silver halide emulsion, those described in Research Disclosure 308119 (hereinafter abbreviated as RD308119) can be used. The following table shows the locations.

[Item] [Page of RD308119] Iodine structure 993 IA section Manufacturing method 993 IA and 994 E crystal habit Normal crystal 993 IA section Twin twin 〃 epitaxial 〃 halogen composition uniform 993 IB Terms Non-uniform 〃 Halogen conversion 994 IC section 置換 Substitution 〃 Metal-containing 994 ID section Monodisperse 995 IF section Solvent addition 項 Latent image forming surface Surface 995 IG section Interior I Applicable photosensitive material Negative 995 I Section H, Positive (including internal fog grains) 用 い る Use mixed emulsion. 995 IJ Desalting 995 II-A In the present invention, the silver halide emulsion is subjected to physical ripening, chemical ripening and spectral sensitization. To use. Additives used in such processes are
No. 17643, No. 18716 and No. 308119 (hereinafter referred to as R
D17643, RD18716 and RD308119).

The following table shows the locations described.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A 23 648 Spectral sensitizer 996 IV-AA, B, C, D, E, H, I, J Item 23-24 648-9 Supersensitizer 996 IV-AE, J Item 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Known photographs that can be used in the present invention Additives for use are also described in Research Disclosure, supra. The following table shows relevant descriptions.

[Item] [Page of RD308119] [RD17643] [RD18716] Anti-turbidity agent 1002 VIII-I 25 650 Dye image stabilizer 1001 VII-J 25 Whitening agent 998 V 24 UV absorber 1003 VIII C , XIII C 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Static inhibitor 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 Matting agent 1007 XVI Developer (contained in photosensitive material) Section 1011 XX-B Various photosensitive materials used in the present invention Couplers can be used, examples of which are described in Research Disclosure, supra. The following table shows relevant descriptions.

[Item] [Page of RD308119] [RD17643] [RD18716] Yellow coupler 1001 VII-D VIIC-G Magenta coupler 1001 VII-D VIIC-G cyan coupler 1001 VII-D VIIC -G DIR coupler 1001 VII-F VII F BAR coupler 1002 VII-F Other useful residue releasing coupler 1001 VII-F Alkali-soluble coupler 1001 VII-E It can be added by the dispersion method described in RD308119XIV and the like.

In the present invention, the aforementioned RD17643 28
The support described in pages RD18716 647-8 and RD308119 XIX can be used.

The light-sensitive materials include the aforementioned RD308119 VII-K
An auxiliary layer such as a filter layer or an intermediate layer described in the section can be provided. The photosensitive material is RD308119 described above.
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in the section VII-K can be adopted.

Next, the photosensitive material for color paper to which the present invention is applied will be described.

As the silver halide grains in the light-sensitive material, silver halide grains mainly containing silver chloride containing at least 80 mol% of silver chloride are used, preferably 90 mol% or more.
Particularly preferably, those containing 95 mol% or more, most preferably 99 mol% or more are used.

The silver chloride emulsion mainly composed of silver chloride may contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride. In this case, the silver bromide content is 20 mol% or less. Is preferably 10 mol% or less, more preferably 3 mol% or less, and when silver iodide is present, it is preferably 1 mol% or less, more preferably 0.5 mol%.
Hereinafter, it is most preferably zero. Such silver chloride 50
Silver halide grains mainly composed of silver chloride consisting of at least
It may be applied to at least one silver halide emulsion layer, but is preferably applied to all photosensitive silver halide emulsion layers.

The crystal of the silver halide grains may be a normal crystal, a twin crystal or any other crystal, and any ratio of [1.0.0] plane to [1.1.1] plane can be used. Furthermore, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layer (phase) -like structure (core-shell type) in which the inside and the outside are different. Good. These silver halides may be of a type in which a latent image is mainly formed on the surface or of a type in which a latent image is formed inside a grain. Further, tabular silver halide grains (JP-A-58-113934)
And Japanese Patent Application No. 59-17070). JP-A-64-26837, JP-A-64-26838, JP-A-64-7
Silver halide described in No. 7047 and the like can be used.

Further, the silver halide grains may be prepared by an acid method,
It may be obtained by any preparation method such as a neutral method or an ammonia method.

Further, for example, a method may be used in which seed particles are formed by an acidic method, and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When growing silver halide grains, controlling the pH, pAg, etc. in the reaction vessel, for example, an amount of silver ion corresponding to the growth rate of silver halide grains as described in JP-A-54-48521. And halide ions are preferably sequentially and simultaneously injected and mixed.

The silver halide emulsion layer of the light-sensitive material processed according to the present invention contains a color coupler.

The red-sensitive layer can contain, for example, a non-diffusible color coupler for producing a cyan partial color image, generally a phenol or α-naphthol coupler. The green-sensitive layer is, for example, at least one non-diffusible color coupler producing a magenta partial color image, usually 5-
It may include a pyrazolone-based color coupler and a pyrazolotriazole. The blue-sensitive layer can include, for example, at least one non-diffusing color coupler that produces a yellow partial color image, generally a color coupler having an open chain ketomethylene group. Color couplers are for example 6, 4
Or it can be a two-equivalent coupler.

In the present invention, a 2-equivalent coupler is particularly preferred.

Suitable couplers are disclosed, for example, in the following publications: Agfa's work report (Mitteilunglnausden)
Forschungslaboratorien der Agfa), Leverkusen / Munchen, Vol.III.p.
111 (1961) "Color coupler" (Farbkuppler) by W. Pelz; K. Venkataraman, "The chemistry of
Synthetic Soy ”(The Chemirsry of Syntheti
c Dyes), Vol. 4, 341-387, Academic Press, "The Theory of the Photographic Process"
graphic Process), 4th edition, pages 353-362; and Research Disclosure No. 1764
3, section VII.

In the present invention, in particular, JP-A-63-106
No. 655, p. 26, a general formula [M-
Magenta couplers represented by the formula (1): Specific examples of these magenta couplers are described in JP-A-63-106655, 2
No. 1 to No. 77 on pages 9 to 34) and 34
Cyan coupler represented by the general formula [C-I] or [C-II] described on page (specific examples of cyan couplers include (C'-1) described in the same specification, pages 37 to 42). ~
(C'-82) and (C ''-1) to (C ''-36)), and high-speed yellow couplers also described on page 20 (specific examples of yellow couplers described in the same specification).
(Y′-1) to (Y′-39) described on pages 21 to 26) are preferred from the viewpoint of the effects of the present invention.

In order to more effectively achieve the object of the present invention, it is preferable to use a magenta coupler represented by the following formula [MI] in the color photographic material according to the present invention.

General formula [MI]

[0102]

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In the magenta coupler represented by
Represents a group of non-metallic atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent.

R represents a hydrogen atom or a substituent.

In the general formula [MI], the substituent represented by R is not particularly limited, but is typically alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl And the like, but in addition to these, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, Carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, and spiro Compound residues, bridged hydrocarbon compound groups and the like are also included.

It may have a substituent represented by R, a group capable of leaving by reaction with an oxidized form of the color developing agent represented by X, a nitrogen-containing heterocyclic ring formed by Z and a ring formed by Z. Preferred ranges and specific examples of the substituents, and preferred ranges of the magenta coupler represented by the general formula [MI] are described in EP 0327272, page 5, line 23 to page 8, line 52.
Same as described in the line.

The following are typical specific examples of the magenta coupler represented by the general formula [MI].

[0109]

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[0110]

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[0111]

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In addition to the typical examples described above, specific examples of the compounds according to the present invention include those described in Japanese Patent Application No. 2-218720, No. 63.
Among the compounds described on pages 82 to 82, Nos. 13, 34, 4
Among the compounds represented by 2,57-59,61,62,65-67 and the compounds described in EP-A-0 327 272, pages 10 to 28, No. 3, 5 to 20, 22 to 33 , 35-60, 62-77 and the compounds described in JP-A-0235913, pp. 36-92, Nos. 1-4, 6, 8-17, 19-24, 26.
~ 43,45 ~ 59,61 ~ 104,106 ~ 121,123 ~ 162,164 ~ 22
The compound represented by 3 can be mentioned.

Further, the above coupler is used in the Journal of the Chemical Society (Journal of the Chemical Society).
Society), Perkin I (1977), 2047-205
2, U.S. Patent 3,725,067, JP-A-59-99437, 58-420
No. 45, No. 59-162548, No. 59-171956, No. 60-33552,
No. 60-43659, No. 60-172982, No. 60-190779, No. 62-2
The compound can be synthesized with reference to 09457 and 63-307453.

The couplers described above can be used in combination with other types of magenta couplers, and are usually 1 × 10 ⁻³ mol to 1 mol, preferably 1 × 10 ⁻² mol to 8 × 10 ⁻ mol per mol of silver halide. It can be used in the range of ¹ mol.

When a nitrogen-containing heterocyclic mercapto compound is used in a light-sensitive material using a silver chloride-based emulsion, not only the effects of the present invention can be achieved well, but also a bleach-fixing solution is mixed in the color developing solution. Impact on the photographic performance that occurs when
Since another effect of making it extremely small is exhibited, it can be cited as a more preferable embodiment in the present invention.

Specific examples of these nitrogen-containing mercapto compounds include (I'-1) to (I'-87) described in JP-A-63-106655, pages 42 to 45.

Silver halide emulsions can be prepared by conventional methods (eg, single or double inflow with constant or rapid acceleration of the material). Particularly preferred is the method of preparation by the dual inflow method while preparing pAg; see Research Disclosure No. 17643, sections I and II.

The silver halide emulsion can be chemically sensitized. Sulfur-containing compounds such as allyl isothiocyanate, allyl thiourea or thiosulfate are particularly preferred. Reducing agents can also be used as chemical sensitizers, such as silver compounds as described in Belgian Patents 493,464 and 568,687, and polyamines or aminomethylsulphonic acid derivatives such as diethylenetriamine according to Belgian Patent 547,323. It is.
Noble metals and noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable sensitizers. This chemical sensitization method is
Fair Bissenshaftriche Photography (Z.
Wiss. Photo.) 46 , 65-72 (1951) in the article by R. Kosiovsky; see also Research Disclosure No. 17643, Section III, supra.

The silver chloride-based emulsion can be prepared by an optically known method,
For example, it can be sensitized using common polymethine dyes such as neuthocyanines, basic or acidic carbocyanines, rhodocyanines, hemicyanines, styryl dyes, oxonols and the like: FM Hamer, FM Hamer. The Cyanine Days and rel. Compounds "(The Cyanine Days and rel
atedCopounds) (1964), p. 431 and following, and Research Disclosure No. 17643, section above
See IV.

The emulsion mainly composed of silver chloride can use conventional antifoggants and stabilizers. Adeindene is a particularly suitable stabilizer, preferably tetra- and penta-adeindene, especially those substituted with a hydroxyl or amino group. Compounds of this type are described, for example, in Birr's article, Zeitschrift für Bissenshaftriche Photography (Z. Wiss. Phot).
o.) 47, 1952, pp. 2-58, and Research Disclosure No. 17643, Section IV above.

The components of the light-sensitive material can be contained by a conventional method; for example, US Pat. No. 2,322,027.
Nos. 2,533,514, 3,689,271, 3,764,336 and 3,765,897. The components of the light-sensitive material, such as couplers and UV absorbers, can also be included in the form of a charged latex; see DE-A-2,541,274 and EP-A-14,921. The components can also be fixed in the light-sensitive material as a polymer; for example, DE-A-2,044,922, U.S. Pat.
See 080,211.

The support of the color photographic light-sensitive material used in the present invention includes, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or combined with a reflector, for example, a glass plate, Examples thereof include a polyester film such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film, and the like, and may be other ordinary transparent supports.

The present invention relates to a color paper such as a color film such as a color paper, a color negative film, a color reversal film, a color reversal paper, a direct positive color paper, a color film for a movie, a color film for a television, etc. It can be applied to photosensitive materials.

[0124]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples of the present invention, but the present invention is not limited to these Examples.

Example 1 Preparation of a silver halide color photographic light-sensitive material (color paper) On a paper support, polyethylene was laminated on one side and polyethylene containing titanium oxide was laminated on the first layer side on the other side. Each layer having the following constitution was applied to form a multilayer silver halide color photographic light-sensitive material. The coating solution was prepared as described below.

First layer coating solution 26.7 g of yellow coupler (Y-1), 100 g of dye image stabilizer (ST-1), 6.67 g of (ST-2), additive (H
Q-1) 0.67 g was dissolved in 6.67 g of a high boiling point solvent (DNP) by adding 60 ml of ethyl acetate, and this solution was dissolved in a 20% surfactant (S
U-1) A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of a 10% aqueous gelatin solution containing 7 ml using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a hardening agent, (H) was added to the second and fourth layers.
-1) and (H-2) were added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

[0129]

[Table 1]

[0130]

[Table 2]

[0131]

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[0132]

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[0133]

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[0134]

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[Method of Preparing Blue-Sensitive Silver Halide Emulsion] 40
(A) in 1000 ml of a 2% aqueous gelatin solution kept at
Solution) and (solution B) with pAg = 6.5 and pH = 3.0.
Add simultaneously over 0 minutes, and further add the following (Solution C) and (Solution D)
Was added simultaneously over 180 minutes while controlling the pH to 7.3 and the pH to 5.5.

At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) 10 g of silver nitrate was added to 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added to 600 ml (D solution) Silver nitrate 300g Water was added and after the addition of 600ml, desalting was performed using 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd. A monodispersed cubic emulsion EMP-1 having a diameter of 0.85 µm, a coefficient of variation in particle size distribution of 7%, and a silver chloride content of 99.5 mol% was obtained.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compounds to obtain a blue-sensitive silver halide emulsion (Em-A).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye (BS-1) 4 × 10 ⁻⁴ mol / Mol AgXX (BS-2) 1 × 10 ⁻⁴ mol / mol AgX [Preparation method of green-sensitive silver halide emulsion] (solution A) and (B
Liquid) and the addition time of (Liquid C) and (Liquid D) in the same manner as EMP-1, except that the average particle diameter was 0.43 μm.
m, variation coefficient of particle size distribution 8%, silver chloride content 99.5 mol%
To obtain a monodispersed cubic emulsion EMP-2.

The following compounds were used for EMP-2.
Chemical ripening was performed at 120 DEG C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye (BS-1) 4 × 10 ⁻⁴ mol / Mol AgX [Method of preparing red-sensitive silver halide emulsion] (solution A) and (B
Liquid) and the addition time of (liquid C) and (liquid D) in the same manner as in EMP-1 except that the average particle size was 0.50 μm.
m, variation coefficient of particle size distribution 8%, silver chloride content 99.5 mol%
Was obtained as a monodispersed cubic emulsion EMP-3.

The following compounds were used for EMP-3.
At 90 ° C. for 90 minutes to obtain a red-sensitive silver halide emulsion (E
m-C).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX Stabilizer (STAB-1) 6 × 10 ^-4 mol / mol Ag
X sensitizing dye (BS-1) 4 × 10 ^-4 mol / mol AgX

[0144]

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This sample was exposed according to a conventional method, and then processed using the following processing steps and processing solutions.

Processing Step Processing Temperature Processing Time Replenishment Amount (1) Color Development 37.5 ± 0.3 ° C. 20 seconds 55 ml / m ² (2) Bleaching and Fixing 37.5 ± 0.5 ° C. 20 seconds 55 ml / m ² (3) Stable (3 tank cascade) 30-34 ° C 90 seconds 248 ml / m ² (4) Drying 60-80 ° C 30 seconds [Color developer] Triethanolamine 10 g Diethylene glycol 10 g N, N-diethylhydroxylamine 3.6 g Hydrazinodiacetic acid 5.0 g Potassium bromide 20 mg Chloride Potassium 2.5g Diethylenetriaminepentaacetic acid 5g Potassium sulfite 0.2g Color developing agent (3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate) 6.0g Potassium carbonate 25g Potassium hydrogen carbonate 5g Add water to make the total volume 1L, and add potassium hydroxide or sulfuric acid.
Adjust to pH 10.10.

[Color Developing Replenisher] Triethanolamine 14.0 g Diethylene glycol 12 g N, N-diethylhydroxylamine 5 g Hydrazinodiacetic acid 7.5
g Potassium chloride 0.1
g Diethylenetriaminepentaacetic acid 7.5 g Potassium sulfite 0.3 g Color developing agent (3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate) 9.8 g Potassium carbonate 30 g Potassium hydrogen carbonate 1 g Add water to make the total volume 1 liter, and add potassium hydroxide or sulfuric acid.
Adjust to pH 10.65.

[Bleach-fixing solution] Ferric organic acid complex salt (described in Table 3) 0.2 mol Ammonium thiosulfate 100 g Sodium sulfite 10 g Sodium metabisulfite 1.5 g Additive (described in Table 3) 3.0 g The mixture is adjusted to pH 1 with 25% aqueous ammonia and acetic acid, and the total volume is adjusted to 1 L.

Bleach-fix replenisher: The concentration of each additive in the bleach-fix was increased by a factor of 1.25, and p
H was used at 5.3.

Stabilizing Solution and Replenisher Orthophenylphenol 0.1 g Ubitex MST (manufactured by Ciba Geigy) 1.0 g ZnSO ₄ 0.2 g ammonium sulfite (40% solution) 5.0 ml 1-hydroxyethylidene-1,1-diphosphonic acid (60% Solution) 5.0 g Ethylenediaminetetraacetic acid 1.5 g Adjust the pH to 7.8 with aqueous ammonia or sulfuric acid and adjust to 1 liter with water.

A running process was performed using the prepared color paper and the processing solution.

In the running process, the automatic developing machine is filled with the above-mentioned color developing tank solution, filled with the bleach-fixing tank solution and the stabilizing tank solution, and while the color paper sample is being processed, the above-mentioned color developing replenisher and bleach-fix replenisher are processed. And a stable replenisher were replenished through a metering pump.

In the running treatment, continuous treatment was carried out until the amount of the bleach-fixing tank liquid replenished in the bleach-fixing tank liquid became three times the volume of the bleach-fixing tank liquid.

After the treatment, the exposed part was divided into two parts, and the remaining one was measured for the amount of residual silver by X-ray fluorescence. Furthermore, the condition of the stain on the edge of the processed color paper at the end of the running test was observed. Further, the state of the bleach-fixing tank liquid (production of sulfide) at the end of the running was visually evaluated.
Table 3 shows the results.

In Table 3, the meanings of the symbols in the column of the state of occurrence of sulfuration are as follows.

◎ No sulfide was observed at all. 極 め て Very little suspended matter was observed on the liquid surface. △ Slight sulfide generation was observed. 明 ら か に Obviously sulfide generation was observed. XX A large amount of sulfide was observed. Occurrence is recognized. The meanings of the symbols in the column of edge stain are as follows.

◎ No edge stains were observed at all. ○ Very slight edge stains were observed. Δ Slight edge stains were observed. × Edge stains were observed to be a serious problem. XX. Extremely edge stains were observed.

[0158]

[Table 3]

In Table 3 and the following tables, EDTA • Fe is ferric ammonium ethylenediaminetetraacetate, PDTA • Fe
Is ferric ammonium 1,3-propylenediaminetetraacetate,
DTPA • Fe is ferric ammonium diethylenetriaminepentaacetate, NTA • Fe is ferric ammonium nitrilotriacetate ,
(A- II-1) .Fe represents ferric ammonium of the exemplary compound (A-II-1). Further, (A-II-3) Fe, (A-I
I-14) Fe, (A-III-1) Fe, (A-III-2) Fe,
(A-III-6) · Fe has the same meaning.

As shown in Table 3, when the ferric complex salt of the organic acid of the present invention is used in combination with the compounds represented by the general formulas [BI] to [B-VII], low replenishment and rapid processing are required. It also shows that there is little residual silver, there is no edge stain, and the storage stability of the bleach-fix solution is good.

[0161] In Example 2 the following examples, the amount of silver halide photographic light-sensitive material is particularly shows the number of grams per 1 m ² unless otherwise noted. Silver halide and colloidal silver are shown in terms of silver. A silver iodobromide color photographic light-sensitive material was prepared as follows.

Silver iodobromide color photographic light-sensitive material A triacetylcellulose film support (75 μm) is subjected to a subbing process on one side (surface), and then sandwiched between the substrates, opposite to the subcoated surface On the side surface (back surface), each layer having the following composition was formed sequentially from the support side.

Back surface first layer Alumina sol AS-100 (aluminum oxide) (manufactured by Nissan Chemical Industries, Ltd.) 0.8 g Back surface second layer Diacetyl cellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle diameter 0.2 μm) 50
mg Next, on the surface of the triacetylcellulose film support subjected to the undercoating process, layers having the following compositions were sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material (a-1).

First layer: Antihalation layer (HC) Black colloidal silver 0.1
5 g UV absorber (UV-1) 0.20 g Colored cyan coupler (CC-1) 0.02 g High boiling solvent (Oil-1) 0.20 g 〃 (Oil-2) 0.20 g Gelatin 1.6 g Second layer; Intermediate layer (IL -1) Gelatin 1.3 g Third layer; low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (average particle size 0.3 μm) 0.4 g 〃 (average particle size 0.4 μm) 0.3 g sensitizing dye (S -1) 3.0 × 10 ^-4 (mol / silver 1 mol) 〃 (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) 〃 (S-3) 0.3 × 10 ^-4 (mol / silver 1 mol) ) Cyan coupler (C-1) 0.50 g 〃 (C-2) 0.20 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006 g 〃 (D-2) 0.01 g High boiling solvent (Oil) -1) 0.55 g gelatin 1.0 g Fourth layer; high-sensitivity red-sensitive emulsion layer (R-H) silver iodobromide emulsion (average particle size 0.7 μm) 0.9 g sensitizing dye (S-1) 1.7 × 10 ^-4 (Mol / silver 1mol) 〃 ( -2) 1.6 × 10 ^-4 (mol / 1 mol of silver) 〃 (S-3) 0.2 × 10 -4 ( mol / mole of silver) Cyan Coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High boiling solvent (Oil-1) 0.30 g Gelatin 1.0 g Fifth layer; Intermediate layer (IL-2) Gelatin 0.8 g Sixth layer; Low-sensitive green-sensitive emulsion layer (G -L) Silver iodobromide emulsion (average particle size 0.4 μm) 0.6 g 〃 (average particle size 0.3 μm) 0.2 g sensitizing dye (S-4) 6.7 × 10 ^-4 (mol / silver 1 mol) 〃 (S -5) 1.0 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (MA) 0.20 g 〃 (MB) 0.40 g Colored magenta coupler (CM-1) 0.10 g DIR compound (D-3) 0.02 g High-boiling solvent (Oil-2) 0.7 g Gelatin 1.0 g Seventh layer; high-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average particle size 0.7 μm) 0.9 g Sensitizing dye (S-6) ) 1.1 × 10 ^-4 Mole / mole of silver) 〃 (S-7) 2.0 × 10 -4 ( mol / 1 mol of silver) 〃 (S-8) 0.5 × 10 -4 ( mol / mole of silver) Magenta coupler (M-A) 0.5 g〃 (MB) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.0
04g High boiling point solvent (Oil-2) 0.35
g Gelatin 1.0 g Eighth layer; Yellow filter layer (YC) Yellow colloidal silver 0.1 g Additive (HS-1) 0.07 g 〃 (HS-2) 0.07 g 〃 (SC-1) 0.12 g High boiling solvent (Oil- 2) 0.15 g gelatin 0.9 g ninth layer; low-sensitivity blue-sensitive emulsion layer (BH) silver iodobromide emulsion (average particle size 0.3 μm) 0.25 g 〃 (average particle size 0.4 μm) 0.25 g sensitizing dye ( S-9) 5.8 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.71 g 〃 (Y-2) 0.30 g DIR compound (D-1) 0.003 g 〃 (D-2) 0.006 g High boiling point solvent (Oil-2) 0.18 g Gelatin 1.2 g 10th layer; high-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (average particle size 0.8 μm) 0.5 g Sensitizing dye (S-10) 3 × 10 ^-4 (mol / silver 1 mol) 〃 (S-11) 1.2 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 g 〃 (Y-2) 0.20 g High boiling solvent (Oil-2) 0.05g gelatin 0.9 g 11th layer; 1st protective layer (PRO-1) Silver iodobromide (average particle size 0.08 μm) 0.3 g UV absorber (UV-1) 0.0
7 g 〃 (UV-2) 0.10 g Additive (HS-1) 0.2 g 〃 (HS-2) 0.1 g High boiling solvent (Oil-1) 0.07 g 〃 (Oil-3) 0.07 g Gelatin 0.85 g 12th layer The second protective layer (PRO-2) compound A 0.04 g compound B 0.004 g polymethyl methacrylate (average particle size 3 μm) 0.02 g methyl methacrylate: ethyl methacrylate: methacrylic acid = 3: 3: 4 (weight ratio) 0.13 g (average particle size: 3 μm) The above color photographic light-sensitive material further comprises a compound Su-
1, Su-2, a viscosity modifier, a hardener H-1, H-2, a stabilizer ST-1, an antifoggant AF-1, AF-2 (with a weight average molecular weight of 10,000 and 110,000), Dye AI
-1, AI-2 and compound DI-1 (9.4 mg / m ² ).

[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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[Preparation of Emulsion] The silver iodobromide emulsion used in the tenth layer was prepared by the following method.

A silver iodobromide emulsion was prepared by a double jet method using monodispersed silver iodobromide grains having an average grain size of 0.33 μm (silver iodide content: 2 mol%) as seed crystals.

The solution <G-1> was heated at a temperature of 70 ° C., a pAg of 7.8, and a pH of
At 7.0, a seed emulsion equivalent to 0.34 mol was added with good stirring.

(Formation of Internal High Iodine Phase-Core Phase-) Then, while maintaining the flow ratio of <H-1> to <S-1> at 1: 1, the accelerated flow rate (the flow rate at the end was 3.6 of initial flow rate
) And added over 86 minutes.

(Formation of External Low Iodine Phase-Shell Phase-) Subsequently, while maintaining pAg 10.1 and pH 6.0, <H-2> and <S
-2> was added at a flow rate accelerated at a flow ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during particle formation were controlled using an aqueous potassium bromide solution and a 56% acetic acid aqueous solution. After the particles were formed, the particles were subjected to a water washing treatment by a conventional flocculation method, and then gelatin was added for redispersion, and the pH and pAg were adjusted to 5.8 and 8.06 at 40 ° C., respectively.

The resulting emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a variation coefficient of grain size distribution of 12.4%, and a silver iodide content of 9.0 mol%.

<G-1> Ossein gelatin 100.0 g 10% by weight methanol solution of compound-1 25.0 ml 28% ammonia aqueous solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finish with water 5000.0 ml <H-1> ossein gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide 90.6 g Finish with water 1030.5 ml <S-1> Silver nitrate 309.2 g 28% aqueous ammonia equivalent Finish with water 1030.5 ml <H-2> Ossein gelatin 302.1 g Potassium bromide 770.0 g Iodine Potassium iodide 33.2 g Finished with water 3776.8 ml <S-2> Silver nitrate 1133.0 g 28% aqueous ammonia solution Equivalent finished with water 3776.8 ml Compound-1

[0182]

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In the same manner, the average grain size, temperature,
The emulsions having different average grain sizes and different silver iodide contents were prepared by changing pAg, pH, flow rate, addition time and halide composition.

All were core / shell type monodispersed emulsions having a variation coefficient of particle size distribution of 20% or less. Each emulsion was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to give a sensitizing dye, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. , 1-phenyl-5-mercaptotetrazole.

The silver iodobromide color photographic material sample was prepared so that the average silver iodide content was 8 mol%.

The thus-prepared light-sensitive material sample was exposed to wedges according to a conventional method, and then subjected to running processing according to the following processing steps. However, the running process is repeated until 2 times the capacity of the bleach tank is replenished (2R).
Performed continuously.

Processing step Processing time Processing temperature Replenishment amount (per 135 siece / 24EX1) (1) Color development (one tank) 3 minutes 15 seconds 38 ° C 18 ml (2) Bleaching and fixing (〃) 30 seconds 38 ° C 3 ml (3 ) Settling (〃) 1 minute 38 ° C 20ml (4) Stabilization (3 tank cascade ゛) 1 minute 38 ° C 40ml (5) Drying (40-80 ° C) 1 minute Color developer 30g potassium carbonate 2.5g sodium bicarbonate Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 0.6 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriamine 3.0 g of pentaacetic acid 1.2 g of potassium hydroxide 1.2 g of water was added to make 1 liter, and the pH was adjusted to 10.00 with potassium hydroxide or 20% sulfuric acid.

Color developing replenisher Potassium carbonate 35 g Sodium bicarbonate 3 g Potassium sulfite 5 g Sodium bromide 0.3 g Hydroxylamine sulfate 3.5 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline Sulfate Salt 6.0 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Water is added to make 1 liter, and the pH is adjusted to 10.20 with potassium hydroxide or 20% sulfuric acid.

Bleaching tank liquid Organic acid ferric complex salt (described in Table 4) 0.35 mol Ethylenediaminetetraacetic acid 10 g Ammonium bromide 1.4 mol Additives (described in Table 4) 3.0 g Glacial acetic acid 50 ml Ammonia water and acetic acid are brought to pH. Adjust to 4.2 and add water to finish to 1 liter.

Bleach replenisher The concentration of each additive in the above-mentioned bleach was made 1.2 times, and the pH was adjusted to 3.0.
Used as

Fixing solution (tank solution and replenisher) Ammonium thiosulfate (70% solution) 350 ml Rhodan ammonium 20 g Anhydrous sodium bisulfite 12 g Sodium metabisulfite 2.5
g Disodium ethylenediaminetetraacetate 0.5 g Water was added to make 1 l, and the pH was adjusted using acetic acid and aqueous ammonia.
Adjust to 6.0.

Stabilizing solution (tank solution and replenishing solution) Hexamethylenetetramine 5 g Diethylene glycol 2 g

[0193]

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The pH was adjusted to 8.0 with KOH, and water was added to add 1
Finish to l.

A running process similar to that of the first embodiment is performed.
The amount of residual silver after processing, the density of yellow fog in the unexposed area, and the state of sulfuration of the fixing solution were evaluated.

The results are summarized in Table 4. In addition, x to ◎ in the table are synonymous with Table 3.

[0197]

[Table 4]

As shown in Table 4, when the ferric complex salt of the organic acid of the present invention and the compounds of the general formulas [BI] to [B-VII] were used in combination, the amount of residual silver was small, and It can be seen that the increase in the yellow fog density of the exposure is small. Further, the storage stability of the fixing solution is good.

[0199] Example 3 chelators be used generally known for photographic, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethyl acid (HEDTA), exemplified compound (A
-II-1), (A-II-3), (A-II-14), (A-
Regarding III-1) and (A-III-6), the degree of biodegradation was determined in accordance with the 301C modified MITI test (I) (adopted on May 12, 1981) in the OECD Chemical Test Guideline.

As a result, the iron salt of the chelating agent of the present invention had extremely good biodegradability, whereas EDTA, DT
The iron salts of PA and HEDTA hardly decomposed, indicating that the chelating agent of the present invention is extremely preferable from the viewpoint of protecting the global environment.

Example 4 The magenta coupler (M-C) in the color paper sample used in Experiments No. 1-12, No. 1-14 and No. 1-20 of Example 1 was used.
C) is an exemplary magenta coupler (M-5), (M-8),
(M-11), (M-9), (M-12), (M-13),
When the same experiment was performed in place of (M-7) and (M-4), the amount of residual silver was improved by 30 to 40%, and an effect of improving the whiteness of the unexposed portion was also recognized.

Example 5 The magenta couplers (MA) and (MB) in the color negative film samples used in Experiment Nos. 2-12, 2-14 and 2-20 in Example 2 were Illustrative magenta coupler (M-
2), (M-6), (M-8), (M-1), (M-1
When the same experiment was performed in place of (0) and (M-3), the amount of residual silver was improved by 30 to 35%, and the yellow fog density was also improved by 50%.

[0203]

According to the present invention, a halogen having a quick desilvering property even at the time of low replenishment, no generation of stains on the edge portion, excellent storage stability of the liquid and excellent biodegradability. A bleaching solution and a bleach-fixing solution for a silver halide color photographic light-sensitive material and a processing method using the same are provided.

Claims (3)

(57) [Claims] 1. The following general formulas [A- II] and [A-III]
And at least one ferric complex salt of a compound represented by the following general formula [BI] to [B-VII]:
The silver halide color photographic light-sensitive material for the bleaching solution or bleach-fixing solution, characterized in that it contains a Kutomo one. Embedded image Wherein A ₁ , A ₂ , A ₃ and A ₄ are each —CH ₂ OH, —PO
₃ (M) ₂ or —COOM, which may be the same or different. M represents a hydrogen atom, an alkali metal atom or another cation. X is an alkylene group having 2 to 6 carbon atoms _{- (B 1 O) n-} B 2 - represents a. n 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. [Chemical formula 2] Wherein A ₁ , A ₂ , A ₃ and A ₄ are each —CH ₂ OH, —PO ₃ (M
² ) ₂ or -COOM ^1, which may be the same or different. M ¹ and M ² represent a hydrogen ion, an alkali metal ion or another cation. X is a linear or branched alkylene group having 2 to 6 carbon atoms, an organic group of a saturated or unsaturated to form a ring, or _{- (B 1 O) n-} B 2 - represents a. n 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. The n1, n2, n3 and n4 represents an integer of 1 or more, is less of Kutomo one may going in each identical is 2 or more. [Chemical formula 3] [In the above general formula, Q represents an atom group necessary for forming a heterocyclic ring containing one or more N atoms (including a heterocyclic ring condensed with at least one 5- or 6-membered unsaturated ring). , A
Is Or an n1 valent heterocyclic residue (including one in which at least one 5- to 6-membered unsaturated ring is fused thereto);
Represents an alkylene group having 1 to 6 carbon atoms, M represents a divalent metal atom, X and X ″ represent ＳS, ＯO or ＮＲNR ″, R ″ represents a hydrogen atom, and has 1 carbon atom. ~ 6 alkyl groups, cycloalkyl groups, aryl groups, heterocyclic residues (5
Represents an amino group, Y represents> N- or> CH-, Z represents a hydrogen atom, an alkali metal atom, or an ammonium group. , An amino group, a nitrogen-containing heterocyclic residue or -S
-BY < (R ⁴ ) (R ⁵ ) , Z ′ represents Z or an alkyl group, R ¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, A ring residue (including at least one 5- to 6-membered unsaturated ring fused thereto) or an amino group; R ² , R ³ , R
^4, R ^5, R and R 'each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, hydroxy group, carboxy group, an amino group,
Represents an acyl group, an aryl group, or an alkenyl group having 1 to 3 carbon atoms. However R ⁴ and R ⁵ may represent -B-SZ, or R and R ', R ² and R ^3, R ⁴ and R ⁵ are cyclized to a heterocyclic residue (5-6 membered each other (Including those in which at least one unsaturated ring is fused thereto). R ⁶ and R ⁷ are each The stands, R ⁹ is alkyl or _{- (CH 2) n8 SO 3} - a represents (wherein R ⁹ is _{- (CH 2) n8 SO 3} - when, l represents 0 or 1.) G ^- is an anion , M1 to m4 and n1
To n8 each represent an integer of 1 to 6; m5 represents an integer of 0 to 6; R ⁸ is a hydrogen atom, an alkali metal atom, Or an alkyl group. However, Q 'has the same meaning as Q described above. D represents a mere bond, an alkylene group having 1 to 8 carbon atoms or a vinylene group, and q represents an integer of 1 to 10.
A plurality of Ds may be the same or different, and a ring formed together with a sulfur atom may be further condensed with a 5- to 6-membered unsaturated ring. X 'is _{-COOM', - OH, -SO 3} M ', - C
_{ONH 2, -SO 2 NH 2,} -NH 2, -SH, -CN, -
^{_{CO 2 R 16, -SO 2 R}} 16, -OR 16, -NR 16 R 17, -
SR ¹⁶ , -SO ₃ R ¹⁶ , -NHCOR ¹⁶ , -NHSO ₂ R
¹⁶ , —OCOR ¹⁶ or —SO ₂ R ¹⁶ , wherein Y ′ is Or m represents a hydrogen atom, and m and n each represent an integer of 1 to 10. R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁷ and R ^{18 each} represent a hydrogen atom, a lower alkyl group, an acyl group or And R ¹⁶ represents a lower alkyl group. R ¹⁹ is -NR
²⁰ R ^21, represent -OR ²² or -SR ^22, R ^13, R ²⁰ and R ²¹ represents a hydrogen atom or a lower alkyl group, R ²² is R
Represents an atomic group necessary for forming a ring by linking with ¹⁸ . R
²⁰ or R ²¹ may combine with R ¹⁸ to form a ring. M '
Represents a hydrogen atom or a cation. The general formula [B
The compounds represented by -I] to [BV] include enolized compounds and salts thereof. ] Wherein the low Do Kutomo one ferric complex salt of the general formula [A- II The compound represented by the general formula [B-
I] - [B-VII] The silver halide color photographic light-sensitive material for the bleaching solution or bleach-fixing solution according to claim 1, characterized in that it contains less Do Kutomo one of the compounds represented by. 3. The general formulas [A-II] and [A-III]
And at least one ferric complex salt of the compound represented by the formula (II) and a small amount of the compound represented by the general formulas (BI) to (B-VII).
The method for processing a silver halide color photographic material, which comprises using a bleaching solution or bleach-fixing solution containing such Kutomo one.