JPH05281684A - Bleaching solution or bleach-fixing solution and method for processing silver halide color photographic sensitive material using same - Google Patents

Abstract

PURPOSE:To provide the bleaching solution or bleach-fixing solution superior in biodegradability and having environmental aptitude by incorporating at least one of the ferric complex salts of specified compounds and at least one of specified compounds. CONSTITUTION:The bleaching or bleach-fixing solution contains at least one of the ferric complex salts of the compounds represented by formula I or the like and at least one of the compounds represented by formula II or the like. In formulae I and II, each of A1-A4 is -H, -OH, -COOM, -PO3(M)2, CH2COOM, -CH2OH, or lower alkyl, and at least one of A1-A4 is -CH2COOM, -COOM, or -PO3M2; each of M, M1, and M2 is H or ammonium group or the like; Q is an atomic group necessary to form a heterocyclic ring containing >=1 N and optionally having at least one 5- or 6-membered unsaturated ring condensed it; and R<1> is H, 1-6C alkyl, or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a 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 property. The present invention relates to a bleaching solution for materials, a bleach-fixing solution, and a method for processing a silver halide color photographic light-sensitive material using them.

[0002]

BACKGROUND OF THE INVENTION Generally, a silver halide color photographic light-sensitive material is 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, a bleaching agent for bleaching silver is added to the bleaching solution and the bleach-fixing solution, which are currently most commonly used for color paper processing, color negative film processing, etc. Is a ferric ethylenediaminetetraacetic acid complex salt. However, the ferric ethylenediaminetetraacetic acid complex salt is biodegradable (Biodegrada).
Poor abilities), if it should flow into rivers or soil, it will accumulate without being decomposed or will drift for a long time, which is not preferable from the standpoint of global environmental protection. Also,
As a bleaching agent that has begun to be used in recent years, for example, JP-A-2-03041
1, 3-propanediaminetetraacetic acid ferric salt (PD) described in JP-A-2-03040, JP-A-63-250651, and the specification.
TA ・ Fe). This PDTA / Fe is a compound having excellent silver bleaching ability, suitability for rapid processing, and excellent biodegradability, but has a practical drawback. That is, when bleaching is performed immediately after color development, bleaching fog occurs, and in order to solve this, a technique of lowering the pH by using acetic acid or the like is considered, but in such a case, odor is a problem. turn into.

Another problem of PDTA / Fe is that it has a strong oxidizing power when it is treated with a fixing solution after the bleaching solution containing PDTA / Fe or when it is used as a bleaching agent for a bleach-fixing solution. The point is that the thiosulfate, which is the fixing agent, is decomposed and sulphurization occurs.

Another bleaching agent is disclosed in JP-A-61-118.
752, JP 61-50145, JP 61-50150, JP 6
The diethylenetriaminepentaacetic acid ferric iron complex salt described in the specification of 1-50147 and the like is known, but even this has a drawback.

Not only is it poorly biodegradable, but it also causes yellow staining at the edges when treating color paper with the bleach. This becomes remarkable especially when the low replenishment process is performed, and becomes a problem that cannot be ignored.

EPO, 430,000A as a bleaching agent with good biodegradability
Compounds described in Japanese Patent No. 1 and German Patent No. 3,939,756 are known, but desilvering performance deteriorates when low replenishment processing is performed using these bleaching agents, resulting in rapid processing performance. 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 having excellent biodegradability and environmental suitability, a bleach-fixing solution, and a method for processing a silver halide light-sensitive material using these processing solutions. Second, there is provided a bleaching solution, a bleach-fixing solution, and a method for processing a silver halide color photographic light-sensitive material using these processing solutions, in which sufficient processing performance can be obtained even at low replenishment processing. The purpose of 3 is to provide a bleaching solution, a bleach-fixing solution which are excellent in rapid processing performance, and a processing method of a silver halide color photographic light-sensitive material using these processing solutions.
A fourth object is to provide a bleaching solution, a bleach-fixing solution and a processing method of a silver halide color photographic light-sensitive material using these processing solutions, which have stable processing performance even at a low processing amount.

Other objects will become apparent in the following specification.

[0009]

The present inventor has arrived at the present invention as a result of extensive research to solve the above problems.

(1) The following general formulas [A-I] and [A-II]
And at least one ferric complex salt of the compound represented by [A-III], and at least one of the compounds represented by the following general formulas [BI] to [B-VII]. A bleaching solution or a bleach-fixing solution for a silver halide color photographic light-sensitive material.

[0011]

[Chemical 9]

[In the formula, A ₁ , A ₂ , A ₃ and A ₄ may be the same or different and each represents a hydrogen atom, a hydroxyl group or -C
_{OOM, -PO 3 (M) 2} , represents a -CH ₂ COOM, -CH ₂ OH or a lower alkyl group. However, at least 1 of A ₁ , A ₂ , A ₃ and A ₄
One is -CH ₂ COOM, -COOM or -PO ₃ (M) ₂ . M, M ₁ and M ₂ each represent a hydrogen atom, an ammonium group, a sodium atom, a potassium atom, a lithium atom or an organic ammonium group. ]

[0013]

[Chemical 10]

[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 of a substituted or unsubstituted 2-6 carbon atoms _{- (B 1 O) n-} B 2 -
Represents. n represents an integer of 1 to 8, and B ₁ and B ₂ may be the same or different, each having 1 to 8 carbon atoms.
5 represents a substituted or unsubstituted alkylene group. ]

[0015]

[Chemical 11]

[Wherein A ₁ , A ₂ , A ₃ and A ₄ are each —CH
₂ OH, —PO ₃ (M ² ) ₂ or —COOM ¹ is shown, and they may be the same or different. M ¹ and M ² represent hydrogen ion, alkali metal ion or other 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 represent integers of 1 or more, and they may be the same or different, and at least one is 2 or more. ]

[0017]

[Chemical 12]

[0018]

[Chemical 13]

[0019]

[Chemical 14]

[0020]

[Chemical 15]

[0021]

[Chemical 16]

(2) At least one ferric complex salt of the compound represented by the general formula [AI] and the general formula [B-
I) to [B-VII] -containing bleaching solution or bleach-fixing solution for a silver halide light-sensitive material according to (1), which contains at least one of the compounds represented by the formulas I to B-VII.

(3) At least one ferric complex salt of the compound represented by the general formula [A-II] and the general formula [B-
A bleaching solution or a bleach-fixing solution for a silver halide color photographic light-sensitive material as described in (1), which contains at least one of the compounds I] to [B-VII].

(4) The above general formulas [A-I] and [A-II]
And a bleaching solution or bleach containing at least one ferric complex salt of the compound represented by [A-III] and at least one of the compounds represented by the following general formulas [BI] to [B-VII]. A method of processing a silver halide color photographic light-sensitive material, which comprises using a fixing solution.

Among these, particularly preferable are the bleaching solution described in (2) above and the bleach-fixing solution described in (3) above.

The present invention will be described in detail below.

In the general formula [A-I], A ₁ , A ₂ , A
₃ and A ₄ may be the same or different and each is a hydrogen atom, a hydroxyl group, —COOM, —PO ₃ (M) ₂ , —CH ₂ OH or a lower alkyl group (a methyl group, an ethyl group, an isopropyl group, n- Propyl group). However, at least one of A ₁ , A ₂ , A ₃ and A ₄ is —COOM or —PO ₃ (M) ₂ . M, M ₁ and M
₂ represents a hydrogen atom, an ammonium group, a sodium atom, a potassium atom, a lithium atom or an organic ammonium group (eg, trimethylammonium group, triethanolammonium group, etc.).

Preferred specific examples of the compound represented by the general formula [AI] are shown below.

[0029]

[Chemical 17]

[0030]

[Chemical 18]

The compounds represented by the general formula [AI] are disclosed in JP-A-63-267750, JP-A-63-267751 and JP-A-2-115172.
No. 2-295954 specification, etc. Among these, a particularly preferable compound part is (A
-I-1) and (A-I-2).

The compound represented by the general formula [A-II] 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 or --COOM. M represents a hydrogen atom, an alkali metal atom (eg sodium, potassium) or another cation (eg ammonium, methylammonium, trimethylammonium, 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 is a hydroxyl group or a carbon number of 1
To alkyl groups (eg, methyl group, ethyl group, etc.) and the like. n represents an integer of 1 to 8, preferably 1
~ 4. Preferred specific examples of the compound represented by the above general formula [A-II] are shown below, but the invention is not limited thereto.

[0034]

[Chemical 19]

[0035]

[Chemical 20]

The compound represented by the above 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 the general formula [A-III] will be described below.

In the formula, A _{1 to} A ₄ may be the same or different and each is --CH ₂ OH, --PO ₃ (M ² ) ₂ or --COOM ¹
Represents. M ¹ and M ² represent hydrogen ion, alkali metal ion (eg sodium ion, potassium ion) or other cation (eg ammonium ion, methylammonium ion, trimethylammonium 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 represents 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, 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 represents an integer of 1 to 8, preferably 1 to 4. Especially preferably, it is 1-2. Preferred specific examples of the compound represented by the above general formula [A-III] are shown below, but the invention is not limited thereto.

[0041]

[Chemical 21]

[0042]

[Chemical formula 22]

[0043]

[Chemical formula 23]

[0044]

[Chemical formula 24]

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

The compound represented by the above 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-I] to [A-III] added is preferably in the range of 0.1 to 2.0 mol per liter of the bleaching solution or the bleach-fixing solution. , And more preferably 0.15 to 1.5 mol.

In the present invention, the bleaching solution or the bleach-fixing solution contains the above-mentioned general formulas [AI] to [A-III] as bleaching agents.
In addition to the iron complex salt of the compound represented by, a ferric iron complex salt of the following compound and the like can be used.

[A'-1] ethylenediaminetetraacetic acid [A'-2] trans-1,2-cyclohexanediaminetetraacetic acid [A'-3] dihydroxyethylglycine [A'-4] ethylenediaminetetrakismethylenephosphonic acid [A] '-5] Nitrilotrismethylenephosphonic acid [A'-6] diethylenetriaminepentakismethylenephosphonic acid [A'-7] diethylenetriaminepentaacetic acid [A'-8] ethylenediaminedioltohydroxyphenylacetic 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 etherdiaminetetraacetic acid [A] to [B] to [B-VII] Specific examples of the compounds include (I-1) to (VII-20) described on pages 79 to 142 of Japanese Patent Application No. 60-256383. Among the compounds represented by the general formulas [BI] to [B-VII], particularly preferable compounds are (B-1) to (B-30) shown below.

[0051]

[Chemical 25]

[0052]

[Chemical formula 26]

[0053]

[Chemical 27]

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

Of the above, the most preferable one is A
A bleaching solution using a ferric complex salt of -I and a bleach-fixing solution using A-II.

The temperature of the bleaching solution or the bleach-fixing solution is preferably 20 to 50 ° C, preferably 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-fixing solution is preferably 5.0 to 9.0, more preferably 6.0 to 8.5.
Is. The pH of the bleaching solution or the bleach-fixing solution is the pH of the processing bath during the processing of the silver halide light-sensitive material, and can be clearly distinguished from the pH of the so-called replenishing solution.

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

A preferred replenishing amount of the bleaching solution or the bleach-fixing solution is 500 ml or less per 1 m ^{2 of the} silver halide color photographic light-sensitive material, more preferably 20 ml to 400 ml, most preferably 40 ml to 350 ml, and a low replenishing amount. The higher the value, the more remarkable the effect of the present invention becomes.

In the present invention, in order to increase the activity of the bleaching solution or the bleach-fixing solution, air may be blown thereinto or oxygen may be blown in the treatment bath and the storage tank of the replenisher for treatment, or a suitable oxidation may be carried out. Agents, such as hydrogen peroxide,
Bromate, persulfate and the like may be added as appropriate.

As the 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 thiocyanate is preferably at least 0.1 mol / l or more, more preferably 0.5 mol / l or more, and particularly preferably 1.0 mol / l or more when processing a color negative film. The content of thiosulfate is preferably at least 0.2 mol / l or more, and more preferably 0.5 mol / l or more when processing a color negative film.

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

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

Further, compounds known to be added to ordinary fixing solutions or bleach-fixing solutions such as alkylamines and polyethylene oxides may be added as appropriate.

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

The processing time with the bleaching solution and the fixing solution is arbitrary, 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.
It is in the range of 20 seconds. The processing time with the bleach-fix solution is 4
Minutes or less are preferable, and more preferably 10 seconds to 2 minutes and 20 seconds.

In carrying out the present invention, the effect of the present invention is better when the ratio of ammonium ion to the total cations in the bleaching solution or the bleach-fixing solution of the present invention is 50 mol% or less. The ratio is more preferably 30 mol% or less, most preferably 10 mol% or less.

In the present invention, it is preferable as an embodiment of the present invention to apply forced liquid agitation to the bleaching solution and the bleach-fixing solution. The reason is that not only the effect of the object of the present invention is better achieved, but also the suitability for rapid processing is improved. Forcible liquid stirring here is not normal liquid stirring movement,
This means that stirring means is added to force stirring.
As the forced stirring means, the means described in JP-A No. 64-222259 and JP-A No. 1-206343 can be adopted.

Further, in the present invention, bleaching which is an effect different from the present invention when the crossover time from the color developing tank to the bleaching tank or the bleach-fixing tank is preferably within 10 seconds, more preferably within 7 seconds. 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 to use substantially no acetic acid.

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

General formula [II] A (-COOM) n In the formula, A represents a valent organic group, n represents an integer of 1 to 6, M represents ammonium, alkali metal (sodium, potassium, lithium, etc.). Or represents a hydrogen atom.

In the general formula [II], the n-valent organic group represented by A is an alkylene group (for example, a methylene group,
Ethylene group, trimethylene group, tetramethylene group, etc.),
Alkenylene group (eg ethenylene group), alkynylene group (eg ethynylene 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 (for example, 1,2,3-propanetriyl group and the like) and an arenetriyl group (for example, 1,2,4-benzenetriyl group and the like).

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

[0075]

[Chemical 28]

[0076]

[Chemical 29]

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

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 liquid,
More preferably, the content is 0.2 to 1.0 mol.

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

Examples of the light-sensitive material include those for color negative film, color paper and color reversal. As the silver halide grains for color negative film, an iodoodor having an average silver iodide content of 3 mol% or more is used. Silver iodide is preferably used, but silver iodobromide containing 4 to 15 mol% of silver iodide is particularly preferable. Above all, the average silver iodide content preferable in the present invention is from 5 mol% to 12 mol%,
Most preferably, it is 8 mol% to 11 mol%.

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

[Item] [Page of RD308119] Iodine structure 993 I-A manufacturing method 993 I-A and 994 E crystal habit normal crystal 993 I-A twin 〃 epitaxial 〃 halogen composition uniform 993 IB Item Non-uniform 〃 Halogen conversion 994 I-C item 〃 Substitution 〃 Metal-containing item 994 I-D item Monodisperse 995 I-F item Solvent addition 〃 Latent image formation surface 995 I-G item Internal 〃 Sensitive material Negative 995 I -H item Positive (including internal fog grains) 〃 Used by mixing emulsions 995 I-J item Desalting 995 II-A item In the present invention, the silver halide emulsion is subjected to physical ripening, chemical ripening and spectral sensitization. Use what you have. The additives used in such a process are Research Disclosure
No.17643, No.18716 and No.308119 (R respectively below
D17643, RD18716 and RD308119).

The places described in the table below are shown.

[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 are also described in Research Disclosure above. The following table shows the relevant locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VIII-I 25 650 Dye image stabilizer 1001 VII-J 25 Whitening agent 998 V 24 UV absorber 1003 VIII C , XIII C Item 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 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 to 27 650 Matting agent 1007 X VI Developer (contained in light-sensitive material) 1011 XX-B Various light-sensitive materials used in the present invention. Couplers can be used, specific examples of which are described in Research Disclosure above. The following table shows the relevant locations.

[Items] [Page of RD308119] [RD17643] [RD18716] Yellow coupler 1001 Item VII-D Item VII C to G Magenta coupler 1001 Item VII-D Item VII C to G Cyan coupler 1001 VII-D Item VII C To 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 The additive used in the present invention is It can be added by the dispersion method described in RD308119XIV.

In the present invention, the aforementioned RD17643 28
The supports described on page RD18716 647-8 and RD308119 XIX can be used.

For the light-sensitive material, the above-mentioned RD308119 VII-K is used.
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 constitutions such as the forward layer, the reverse layer and the unit constitution described in the item VII-K can be adopted.

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

As the silver halide grains in the photographic 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 are used, and most preferably those containing 99 mol% or more.

The silver halide emulsion mainly containing silver chloride can 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 preferable, more preferably 10 mol% or less, further preferably 3 mol% or less, and when silver iodide is present, it is preferably 1 mol% or less, more preferably 0.5 mol%.
Below, it is most preferably zero. Such silver chloride 50
The silver halide grains mainly composed of silver chloride containing more than mol% are
It may be applied to at least one silver halide emulsion layer, but is preferably applied to all light-sensitive silver halide emulsion layers.

The crystals of the silver halide grains may be normal crystals, twin crystals or other crystals, and any ratio of [1.0.0] plane to [1.1.1] plane can be used. Further, 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) having different inside and outside. Good. Further, 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 the latent image is formed inside the grain. Further, tabular silver halide grains (JP-A-58-113934)
Japanese Patent Application No. 59-170070). Further, JP-A 64-26837, 64-26838, 64-7
The silver halide described in 7047 etc. can be used.

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

Alternatively, 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 them to a predetermined size. When growing the silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled, and the amount of silver ions corresponding to the growth rate of the silver halide grains as described in JP-A-54-48521 is used. It is preferable to sequentially and simultaneously inject and mix halide ions with halide ions.

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, non-diffusible color couplers which produce cyan partial color images, generally phenol or α-naphthol based couplers. The green-sensitive layer is, for example, at least one non-diffusible color coupler, usually 5-, which produces a magenta partial color image.
A pyrazolone color coupler and a pyrazolotriazole can be included. The blue-sensitive layer can contain, for example, at least one non-diffusible color coupler that produces a yellow partial color image, typically a color coupler having open chain ketomethylene groups. Color couplers are 6, 4
Or it can be a two equivalent coupler.

In the present invention, 2-equivalent couplers are particularly preferable.

Suitable couplers are disclosed, for example, in the following publications: Agfa's research report (Mitteilunglnausden).
Forschungslaboratorien der Agfa), Leverkusen / Munchen, Vol.III.p.
111 (1961) Naka W. Pelz's "Color Coupler"(Farbkuppler); K. Venkataraman (K. Venkataraman), "The Chemistry of the
Synthetic Soybean "(The Chemirsry of Syntheti
C Dyes), Vol. 4, 341-387, Academic Press, "The Theory of the Photographic Process"
Graphic Process), 4th edition, pp. 353-362; and Research Disclosure No. 1764
3, section VII.

In the present invention, in particular, JP-A-63-106 is used.
No. 655, page 26.
1]] (Specific examples of these magenta couplers are disclosed in JP-A-63-106655, 2
No. 1 to No. 77 described on pages 9 to 34) and 34
Cyan couplers represented by the general formula [C-I] or [C-II] described on page 37 (Specific examples of cyan couplers include (C'-1) described on pages 37 to 42 of the same specification. ~
(C'-82), (C ''-1) to (C ''-36)), and high speed yellow couplers also described on page 20 (specifically exemplified yellow couplers).
(Y'-1) to (Y'-39) described on pages 21 to 26 are preferably used from the viewpoint of the effect of the object of the present invention.

Further, in order to more effectively achieve the object of the present invention, it is preferable to use a magenta coupler represented by the following general formula [MI] in the color light-sensitive material of the present invention.

General formula [MI]

[0102]

[Chemical 30]

In the magenta coupler represented by
Represents a non-metal atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent.

R represents a hydrogen atom or a substituent.

In the above formula [M-I], the substituent represented by R is not particularly limited, but typically, alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl. Other groups such as halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, and the like. Carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups, and spiro. A compound residue, a bridged hydrocarbon compound group, etc. are also mentioned.

The substituent represented by R, the group represented by X which can be split off by the reaction with the oxidation product of the color developing agent, the nitrogen-containing heterocycle formed by Z and the ring formed by Z may have. The preferred range and specific examples of the substituents, and the preferred range of the magenta coupler represented by the general formula [MI] are described in European Patent Publication No. 0327272, page 5, line 23 to page 8, page 52.
It is the same as that described in the row.

Typical specific examples of the magenta coupler represented by the formula [MI] are shown below.

[0109]

[Chemical 31]

[0110]

[Chemical 32]

[0111]

[Chemical 33]

In addition to the representative examples described above, specific examples of the compound according to the present invention include No. 63 of Japanese Patent Application No. 2-218720.
Among the compounds described on pages 82 to 82, No. 13, 34, 4
2,57 to 59,61,62,65 to 67, compounds disclosed in European Patent Publication No. 0327272, pages 10 to 28, No. 3,5 to 20,22 to 33 , 35-60, 62-77 and the compounds described in No. 0235913, pages 36-92, Nos. 1-4, 6, 8-17, 19-24, 26.
~ 43, 45 ~ 59, 61 ~ 104, 106 ~ 121, 123 ~ 162, 164-22
The compound shown by 3 can be mentioned.

Further, the coupler is a Journal of The Chemical Society.
Society), Perkin I (1977), 2047-205
2, U.S. Patent 3,725,067, JP-A-59-99437, 58-420
45, 59-162548, 59-171956, 60-33552,
60-43659, 60-172982, 60-190779, 62-2
It can be synthesized with reference to 09457 and 63-307453.

[0114] aforementioned couplers can also be used with other types of magenta couplers, usually 1 mol of silver halide per 1 × 10 ^-3 mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^- 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 an emulsion mainly composed of silver chloride, not only the effect of the present invention is satisfactorily achieved, but also a bleach-fixing solution is mixed in a color developing solution. The effect on photographic performance that occurs when
Since it has another effect of making it extremely slight, it can be mentioned as a more preferable embodiment in the present invention.

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

The silver halide emulsions can be prepared by conventional methods (eg, single or double inflow with constant or accelerated rush of material). The double inflow method of preparing pAg is particularly preferred; 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. Recycling agents can also be used as chemical sensitizers, such as silver compounds as described in, for example, Belgian Patents 493,464 and 568,687, and polyamines such as diethylenetriamine or aminomethyl sulfonic acid derivatives as described in Belgian Patent 547,323. Is.
Noble metals and noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable sensitizers. This chemical sensitization method
Fair Bissen Schalich Photography (Z.
Wiss. Photo.) 46 , 65-72 (1951) in the article by R. Kosiovsky; see also Research Disclosure No. 17643, section III above.

An emulsion mainly composed of silver chloride is an optically known method,
It can be sensitized with the usual polymethine dyes such as neutraocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like: FM Hamer. Cyanine soybean and related compounds "(The Cyanine Days and rel
atedCopounds) (1964), p. 431 and following, and above Research Disclosure No. 17643, section.
See IV.

For the emulsion mainly containing silver chloride, conventional antifoggants and stabilizers can be used. Adeindene is a particularly suitable stabilizer, tetra- and penta-adeneindene are preferred, especially those substituted with hydroxyl or amino groups. Compounds of this type are described, for example, in Birr's paper, Zeitschrift-Für-Bissen-Schagliche Photography (Z.Wiss.Phot).
o.) 47, 1952, p.2-58, and Research Disclosure No. 17643, supra, Section IV.

The components of the light-sensitive material can be incorporated by a conventional known 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 charged latices; see DE-A 2,541,274 and EP-A 14,921. The components can also be fixed in the light-sensitive material as polymers; for example, DE-A 2,044,922, US Pat. Nos. 3,370,952 and 4,
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 a reflector in combination, such as a glass plate, Examples thereof include a polyester film such as cellulose acetate, cellulose nitrate, or polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film, and the like, and other usual transparent supports may be used.

The present invention can be applied to color films such as color papers, color negative films, color reversal films, color reversal papers, direct positive color papers, color films for movies, color films for televisions, etc. which are used for general use or for movies. 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 silver halide color photographic light-sensitive material (color paper) A paper support was laminated on one side with polyethylene and on the other side with polyethylene containing titanium oxide on the first layer side. Each layer having the constitution shown below was applied to prepare a multilayer silver halide color photographic light-sensitive material. The coating liquid was prepared as follows.

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
0.6-1 g of Q-1) was dissolved in 6.67 g of high boiling point solvent (DNP) by adding 60 ml of ethyl acetate, and this solution was dissolved in 20% surfactant (S
U-1) 220 ml of 10% gelatin aqueous solution containing 7 ml was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a coating solution for the first layer.

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, the second and fourth layers (H
-1) and (H-2) were added to the 7th layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

[0129]

[Table 1]

[0130]

[Table 2]

[0131]

[Chemical 34]

[0132]

[Chemical 35]

[0133]

[Chemical 36]

[0134]

[Chemical 37]

[Method for preparing blue-sensitive silver halide emulsion] 40
In 1000 ml of 2% gelatin aqueous solution kept at ℃, the following (A
Liquid 3) and (B liquid) are controlled to pH = 6.5 and pH = 3.0.
Simultaneously added over 0 minutes, and further the following (solution C) and (solution D)
Was simultaneously added over 180 minutes while controlling pH = 7.3 and pH = 5.5.

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

(Solution A) Sodium chloride 3.42g Potassium bromide 0.03g Water added 200ml (Solution B) Silver nitrate 10g Water added 200ml (Solution C) Sodium chloride 102.7g Potassium bromide 1.0g Water added 600ml (Solution D) After adding 300 g of silver nitrate and adding 600 ml of water, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size. A monodisperse cubic emulsion EMP-1 having a diameter of 0.85 μm, a variation coefficient of the grain size distribution of 7% and a silver chloride content of 99.5 mol% was obtained.

The above emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound 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 AgX 〃 (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 (C liquid) and (D liquid) were changed in the same manner as in EMP-1, except that the average particle size was 0.43 μm.
m, variation coefficient of particle size distribution 8%, silver chloride content 99.5 mol%
To obtain a monodisperse cubic emulsion EMP-2.

The following compounds were used for EMP-2:
Chemical ripening was carried out at 120 ° 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 / Molar AgX [Method for preparing red-sensitive silver halide emulsion] (solution A) and (B
(Liquid) and the addition time of (C liquid) and (D liquid) are changed in the same manner as in EMP-1, except that the average particle size is 0.50 μm.
m, variation coefficient of particle size distribution 8%, silver chloride content 99.5 mol%
To obtain a monodisperse cubic emulsion EMP-3.

The following compounds were used for EMP-3:
Chemical ripening at 90 ° C for 90 minutes to give a red-sensitive silver halide emulsion (E
m-C) was obtained.

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]

[Chemical 38]

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

Treatment process Treatment temperature Treatment time Replenishment amount (1) Color development 37.5 ± 0.3 ° C. 20 seconds 55 ml / m ² (2) Bleach fixing 37.5 ± 0.5 ° C. 20 seconds 55 ml / m ² (3) Stable (3 tank cascade) 30-34 ℃ 90 seconds 248ml / m ² (4) Dry 60-80 ℃ 30 seconds [Color developer] Triethanolamine 10g Diethylene glycol 10g N, N-Diethylhydroxylamine 3.6g Hydrazinodiacetic acid 5.0g Potassium bromide 20mg 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 Add 5g water to make the total volume 1 L and add potassium hydroxide or sulfuric acid.
Adjust to pH 10.10.

[Color development 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 7.5g Potassium sulfite 0.3g Color developing agent (3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate) 9.8g Potassium carbonate 30g Potassium hydrogencarbonate 1g Add water to bring the total volume to 1 liter and add potassium hydroxide or sulfuric acid.
Adjust to pH 10.65.

[Bleach-fixing solution] Organic acid Ferric complex salt (listed in Table 3) 0.2 mol Ammonium thiosulfate 100 g Sodium sulfite 10 g Sodium metabisulfite 1.5 g Additive (listed in Table 3) 3.0 g Make up to 1 liter, adjust the pH to 7.0 with 25% aqueous ammonia and acetic acid, and make up to 1 liter.

Bleach-fixing replenisher The concentration of each additive in the bleach-fixing solution is increased to 1.25 times, and p
H was set to 5.3 and used.

Stabilizer and Replenisher Orthophenylphenol 0.1 g Ubitex MST (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 to 1 liter with water.

A running treatment was carried out using the color paper and the treatment liquid thus prepared.

In the running process, the automatic developing machine was filled with the above-mentioned color developing tank solution and the bleach-fixing tank solution and the stabilizing tank solution, and the above-mentioned color developing replenishing solution and bleach-fixing replenishing solution were prepared while processing the color paper sample. And the stable replenisher was replenished with a metering pump.

The running treatment was carried out continuously until the amount of the bleach-fixing tank solution replenished in the bleach-fixing tank solution became three times the volume of the bleach-fixing tank solution.

After the treatment, the exposure-exposed area was divided into two, and the amount of residual silver was measured by fluorescent X-ray. Furthermore, the state of stains on the edge of the treated color paper at the end of the running test was observed. Further, the appearance of the bleach-fixing tank liquid (production of sulfide) at the end of running was visually evaluated.
The results are shown in Table 3.

In Table 3, the meanings of the symbols in the column of the occurrence status of sulfurization are as follows.

◎ No sulfides are observed. ○ Very slight floating substances are observed on the liquid surface. △ Slight sulfides are observed. × Clear sulfides are observed. × × A large amount of sulfides is observed. Occurrence is recognized. The symbols in the edge stain column have the following meanings.

◎ No edge stains are observed. ○ Very slight edge stains are observed. △ Slight edge stains are observed. × Edge stains are recognized to be a problem. × × Significant edge stains are observed.

[0158]

[Table 3]

In Table 3 and the following table, EDTA.Fe is ethylenediaminetetraacetic acid ferric ammonium, PDTA.Fe.
Is 1,3-propylenediaminetetraacetic acid ferric ammonium,
DTPA / Fe is diethylenetriaminepentaacetic acid ferric ammonium, NTA / Fe is nitrilotriacetic acid ferric ammonium,
(A-I-1) .Fe is ferric ammonium of the exemplified compound (A-I-1), and (A-I-2) .Fe is the exemplified compound (A-I-).
2) ferric ammonium and (A-II-1) .Fe represent ferric ammonium of the exemplified compound (A-II-1). Furthermore, (A-II-3) .Fe, (A-II-14) .Fe, (A-III-
1) .Fe, (A-III-2) .Fe, and (A-III-6) .Fe have the same meaning.

From Table 3 above, when the ferric iron complex salt of the organic acid of the present invention and the compound represented by the general formulas [BI] to [B-VII] are used in combination, a low replenishment is required at the time of rapid processing. It was also found that there is little residual silver, there is no edge stain, and the storability of the bleach-fix solution is good.

Example 2 In the following examples, the addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver. A silver iodobromide color photographic light-sensitive material was prepared in the following manner.

Silver iodobromide color photographic light-sensitive material Triacetylcellulose film A support (75 μm) was subjected to undercoating on one side (front surface), and then sandwiched between the support and the surface opposite to the undercoated surface. Each layer having the composition shown below was sequentially formed on the side surface (back surface) from the support side.

Backside first layer Aluminasol AS-100 (aluminum oxide) (manufactured by Nissan Chemical Industries, Ltd.) 0.8 g Backside second layer diacetyl cellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle size 0.2 μm) 50
mg Then, each layer having the composition shown below was sequentially formed from the support side on the surface of the triacetyl cellulose film support which was subjected to the subbing process to prepare a multilayer color photographic light-sensitive material (a-1).

First Layer: Antihalation Layer (HC) Black Colloidal Silver 0.1
5g UV absorber (UV-1) 0.20g Colored cyan coupler (CC-1) 0.02g High boiling point solvent (Oil-1) 0.20g 〃 (Oil-2) 0.20g Gelatin 1.6g Second layer; Intermediate layer (IL -1) Gelatin 1.3g Third layer; low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (average grain size 0.3 μm) 0.4 g 〃 (average grain 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 point solvent (Oil) -1) 0.55 g Gelatin 1.0 g Fourth layer; high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain size 0.7 μm) 0.9 g Sensitizing dye (S-1) 1.7 × 10 ^-4 (Mol / silver 1 mol) 〃 ( -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 point solvent (Oil-1) 0.30 g Gelatin 1.0 g Fifth layer; Intermediate layer (IL-2) Gelatin 0.8 g Sixth layer; Low sensitivity green sensitive emulsion layer (G -L) Silver iodobromide emulsion (average grain size 0.4 μm) 0.6 g 〃 (average grain 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 point solvent (Oil-2) 0.7g Gelatin 1.0g 7th layer; high-sensitivity green sensitive emulsion layer (GH) Silver iodobromide emulsion (average grain size 0.7 μm) 0.9g 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) 0.13g Colored magenta coupler (CM-1) 0.04g DIR compound (D-3) 0.0
04g High boiling point solvent (Oil-2) 0.35
g Gelatin 1.0g Eighth layer; Yellow filter layer (YC) Yellow colloidal silver 0.1g Additive (HS-1) 0.07g 〃 (HS-2) 0.07g 〃 (SC-1) 0.12g High boiling point solvent (Oil- 2) 0.15g gelatin 0.9g 9th layer; low-sensitivity blue-sensitive emulsion layer (B-H) silver iodobromide emulsion (average grain size 0.3 μm) 0.25 g 〃 (average grain 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) 0.18g Gelatin 1.2g 10th layer; high-sensitivity blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (average grain size 0.8 µm) 0.5g 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 point solvent (Oil-2) 0.05g gelatin 0.9g 11th layer; 1st protective layer (PRO-1) Silver iodobromide (average particle size 0.08 μm) 0.3g Ultraviolet absorber (UV-1) 0.0
7g 〃 (UV-2) 0.10g Additive (HS-1) 0.2g 〃 (HS-2) 0.1g High boiling point solvent (Oil-1) 0.07g 〃 (Oil-3) 0.07g Gelatin 0.85g 12th layer Second protective layer (PRO-2) Compound A 0.04g Compound B 0.004g Polymethylmethacrylate (average particle size 3 μm) 0.02g Methylmethacrylate: ethylmethacrylate: methacrylic acid = 3: 3: 4 (weight ratio) 0.13 g of the copolymer (average particle size 3 μm) The above-mentioned color photographic light-sensitive material further comprises the compound Su-
1, Su-2, viscosity modifiers, hardeners H-1, H-2, stabilizers ST-1, antifoggants AF-1, AF-2 (weight-average molecular weights of 10,000 and 1100,000), Dye AI
-1, AI-2 and compound DI-1 (9.4 mg / m ² ).

[0165]

[Chemical Formula 39]

[0166]

[Chemical 40]

[0167]

[Chemical 41]

[0168]

[Chemical 42]

[0169]

[Chemical 43]

[0170]

[Chemical 44]

[0171]

[Chemical 45]

[0172]

[Chemical 46]

[0173]

[Chemical 47]

[Preparation of Emulsion] The silver iodobromide emulsion used in the 10th layer was prepared by the following method.

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

The solution <G-1> was heated at a temperature of 70 ° C., a pAg of 7.8 and a pH of
The seed emulsion corresponding to 0.34 mol was added while maintaining the ratio at 7.0 while stirring well.

(Formation of Internal High Iodity Phase-Core Phase) After that, with the flow rate ratio of <H-1> and <S-1> kept at 1: 1, the accelerated flow rate (the flow rate at the end is Initial flow rate of 3.6
Doubling) and added over 86 minutes.

(Formation of External Low Iodity Phase-Shell Phase) Subsequently, <H-2> and <S> while maintaining pAg 10.1 and pH 6.0.
-2> was added at a flow rate accelerated by a flow rate 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 grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution. After the particles were formed, they were washed with water by a conventional flocculation method, and then gelatin was added to redisperse them, and pH and pAg were adjusted to 5.8 and 8.06 at 40 ° C., respectively.

The obtained 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> 100.0 g of ossein gelatin 10% by weight solution of compound-1 in methanol 25.0 ml 28% aqueous ammonia 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 151.6g Potassium iodide 90.6g Finish with water 1030.5ml <S-1> Silver nitrate 309.2g 28% aqueous ammonia solution Equivalent with water 1030.5ml <H-2> Ocein gelatin 302.1g Potassium bromide 770.0g Iodine Potassium iodide 33.2g Finish with water 3776.8ml <S-2> Silver nitrate 1133.0g 28% aqueous ammonia solution Equivalent Finish with water 3776.8ml Compound-1

[0182]

[Chemical 48]

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

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

However, the above silver iodobromide color photographic light-sensitive material sample was prepared so that the average silver iodide content was 8 mol%.

The photosensitive material sample thus prepared was subjected to wedge exposure according to a conventional method, and then running processing was performed according to the following processing steps. However, the running process is repeated until the volume of the bleaching tank is doubled (2R),
It went continuously.

Treatment process Treatment time Treatment temperature Replenishment amount (135 size 24EX1 true) (1) Color development (1 tank) 3 minutes 15 seconds 38 ° C 18ml (2) Bleach fixing (〃) 30 seconds 38 ° C 3ml (3) ) Settling (〃) 1 minute 38 ℃ 20ml (4) Stabilization (3 tank Cascade) 1 minute 38 ℃ 40ml (5) Dry (40-80 ℃) 1 minute Color developer 30g potassium carbonate 2.5g sodium bicarbonate Potassium sulfite 3.0g Sodium bromide 1.3g Potassium iodide 0.6mg Hydroxylamine sulfate 2.5g Sodium chloride 0.6g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5g Diethylenetriamine Pentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water is added to make 1 liter, and the pH is adjusted to 10.00 using potassium hydroxide or 20% sulfuric acid.

Color development replenishing solution Potassium carbonate 35 g Sodium hydrogen carbonate 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 Sulfuric acid 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 (listed in Table 4) 0.35 mol Ethylenediaminetetraacetic acid 10 g Ammonium bromide 1.4 mol Additive (listed in Table 4) 3.0 g Glacial acetic acid 50 ml pH of ammonia water and acetic acid Adjust to 4.2 and add water to make 1 liter.

Bleach Replenisher The concentration of each additive in the above bleaching solution was 1.2 times, and the pH was 3.0.
Used as.

Fixer (tank and replenisher) Ammonium thiosulfate (70% solution) 350 ml Ammonium rhodanate 20 g Anhydrous sodium bisulfite 12 g Sodium metabisulfite 2.5
g Ethylenediaminetetraacetic acid disodium 0.5g Add water to make 1 liter, and add acetic acid and ammonia water to adjust the pH.
Adjust to 6.0.

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

[0193]

[Chemical 49]

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

The same running process as in Example 1 was performed,
The amount of residual silver after the processing, the yellow fog density in the unexposed area, and the sulfurization state of the fixing solution were evaluated.

The results are summarized in Table 4. In addition, x to ⊚ in the table have the same meaning as in Table 3.

[0197]

[Table 4]

From Table 4 above, when the ferric iron 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 residual silver amount was small, and It can be seen that the increase in yellow fog density during exposure is small. Furthermore, the storage stability of the fixer is also good.

Example 3 Chelating agents commonly used for photography, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), N-hydroxyethylethylenediaminetriacetic acid (HEDTA), exemplified compounds ( A
-I-1), (A-I-2), (A-II-1), (A-II
-3), (A-II-14), (A-III-1) and (AI)
Regarding II-6), the biodegradability was determined according to the 301C modified MITI test (I) of the OECD test guideline for chemicals (adopted May 12, 1981).

As a result, the iron salt of the chelating agent of the present invention has extremely good biodegradability, while EDTA and DT
It was found that the iron salts of PA and HEDTA are hardly decomposed, and the chelating agent of the present invention is extremely preferable from the viewpoint of protecting the global environment.

Example 4 Magenta coupler (M- in the color paper sample used in Experiment Nos. 1-12, No. 1-14 and No. 1-20 of Example 1)
C) are illustrated as magenta couplers (M-5), (M-8),
(M-11), (M-9), (M-12), (M-13),
When the same experiment was performed by replacing (M-7) and (M-4) respectively, the residual silver amount was improved by 30 to 40%, and the effect of improving the whiteness of the unexposed area was also recognized.

Example 5 The magenta couplers (MA) and (MB) in the color negative film samples used in Experiment Nos. 2-12, No. 2-14 and No. 2-20 of Example 2 were compared. Illustrative magenta coupler (M-
2), (M-6), (M-8), (M-1), (M-1)
When the same experiment was carried out by substituting 0) and (M-3) respectively, the residual silver amount was improved by 30 to 35%, and the yellow fog density was also improved by 50%.

[0203]

According to the present invention, a halogen which has a rapid desilvering property even at a low replenishment rate, does not cause edge stains, has excellent storage stability of a liquid, and has excellent biodegradability. Provided are a bleaching solution for a silver halide color photographic light-sensitive material, a bleach-fixing solution and a processing method using these.

Claims (4)

[Claims] 1. At least one ferric complex salt of a compound represented by the following general formulas [AI], [A-II] and [A-III] and the following general formulas [BI] to [B]. -VII] A bleaching solution or a bleach-fixing solution for a silver halide color photographic light-sensitive material, which contains at least one compound represented by the formula [VII]. [Chemical 1] [In the formula, A ₁ , A ₂ , A ₃ and A ₄ may be the same or different and each represents a hydrogen atom, a hydroxyl group, -COOM, -PO ₃ (M)
₂ , -CH ₂ COOM, -CH ₂ OH or a lower alkyl group is represented. However, at least one of A ₁ , A ₂ , A ₃ and A ₄ is —CH ₂ COO.
M, is a -COOM or -PO ₃ (M) _2. M, M ₁ and M ₂ each represent a hydrogen atom, an ammonium group, a sodium atom, a potassium atom, a lithium atom or an organic ammonium group. ] [Chemical 2] [In the formula, A ₁ , A ₂ , A ₃ and A ₄ are —CH ₂ OH and —PO, respectively.
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 3] [In the formula, A ₁ , A ₂ , A ₃ and A ₄ are respectively —CH ₂ OH, —PO ₃ (M
² ) ₂ or -COOM ^1, which may be the same or different. M ¹ and M ² represent hydrogen ion, alkali metal ion or other 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 represent integers of 1 or more, and they may be the same or different, and at least one is 2 or more. ] [Chemical 4] [Chemical 5] [Chemical 6] [Chemical 7] [Chemical 8] 2. At least one ferric complex salt of the compound represented by the general formula [AI] and the general formula [BI].
A bleaching solution or a bleach-fixing solution for a silver halide color photographic light-sensitive material according to claim 1, which contains at least one of the compounds represented by [B-VII]. 3. At least one ferric complex salt of the compound represented by the general formula [A-II] and the general formula [BI].
A bleaching solution or a bleach-fixing solution for a silver halide color photographic light-sensitive material according to claim 1, which contains at least one of the compounds represented by [B-VII]. 4. At least one of ferric complex salts of the compounds represented by the general formulas [AI], [A-II] and [A-III], and the following general formulas [BI] to [B]. -VII] A method for processing a silver halide color photographic light-sensitive material, which comprises using a bleaching solution or a bleach-fixing solution containing at least one compound represented by the formula [VII].