JPH05232655A - Bleaching liquid for silver halide color photographic sensitive material and treatment using this bleaching liquid - Google Patents

Abstract

PURPOSE:To improve biodegradability by incorporating a ferric (III) complex salt of a specified compd. and bromide and specifying the molar ratio of the bromide ion concn. to iron ion concn. CONSTITUTION:This color photographic sensitive material contains at least bromide and at least one of ferric (III) complex salt of compd. expressed by formula I, II, III or IV. The molar ratio of (bromide ion concn.)/(iron ion concn.) is specified to <=2.5. In formulae, A1-A4 are hydrogen atom, -CH2COOM3, etc., M1-M3 are hydrogen atom, alkali metal atom, etc., A5-A8 are -CH2OH, -COOM4, etc., M4 is hydrogen atom, alkali metal atom, etc., X1 is alkylene group of 2-6 carbon number, A9-A12 are -COOM5, -CH2OH, etc., M5 is hydrogen atom, alkali metal atom, etc., X2 is alkylene group of 2-6 carbon number, A13-A16 are -CH2OH, -COOM7, etc., M7 is hydrogen atom, alkali metal atom, etc., and X3 is alkylene group of 3-6 carbon number.

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 (hereinafter also simply referred to as "color light-sensitive material"), and more specifically, it has excellent biodegradability and rapid processing. TECHNICAL FIELD The present invention relates to a bleaching solution for a color light-sensitive material having excellent properties and a method for processing a color light-sensitive material using the same.

[0002]

BACKGROUND OF THE INVENTION Generally, a color light-sensitive material is a color developing solution,
Processing is performed with a bleaching solution, a fixing solution, a stabilizing solution, and the like. Among these processing solutions, a bleaching agent for bleaching silver is added to the bleaching solution. Currently, the most commonly used bleaching agent for color negative films and color papers is ethylenediaminetetraacetic acid. It is an iron complex salt.

However, the ferric ethylenediaminetetraacetic acid complex is poor in biodegradability, and when it flows into a river or soil, it will not be decomposed and will be accumulated or will drift over a long period of time. Not desirable from the standpoint of protection.

On the other hand, in recent years, attempts have been made to shorten the processing time and speed up the processing, but it is difficult to shorten the processing time because ethylenediaminetetraacetic acid ferric iron complex salt has a weak bleaching power.

As an attempt to shorten the treatment time, it is possible to shorten the treatment time to some extent by increasing the concentration of the ferric ethylenediaminetetraacetic acid complex salt which is a bleaching agent and the concentration of bromide which is a halogenating agent. , There is a limit in solubility,
Moreover, increasing the concentration itself is not preferable from the viewpoint of environmental protection.

Further, as a bleaching agent which has recently begun to be used, for example, JP-A-2-03041, JP-A-2-03040 and JP-A-63-250651.
1,3-Propanediaminetetraacetic acid ferric salt (PDTA.Fe) described in Japanese Patent No. 3,089,049. This PDTA / Fe is a compound having excellent biodegradability. Furthermore, as a bleaching agent with good biodegradability, EP 0,430,000 A1 and German Patent 3,93
The compounds described in 9,756 and the like are known.

However, even if these ferric iron complex salts having good biodegradability are used, they are still insufficient in terms of silver bleaching ability.
There is a limit when trying to accelerate further.

Further, when the bromide ion concentration is increased, tar is likely to be generated in the treatment liquid tank during continuous treatment and concentration is likely to occur, and crystal precipitation is likely to occur particularly in the aeration unit, which is a problem. ..

These problems become more remarkable during the low replenishment process or the recycling process.

[0010]

SUMMARY OF THE INVENTION Therefore, a first object of the present invention is to provide a bleaching solution having excellent biodegradability and environmental suitability, and a method for processing a color light-sensitive material using the bleaching solution. It is intended to provide a bleaching solution which is capable of obtaining sufficient processing performance at any time and is free from tar and crystal precipitation, and a method for processing a color light-sensitive material using the same. Other purposes will become apparent in the text below.

[0011]

The above objects of the present invention have been achieved by the following configurations. That is, (1) contains at least one ferric complex salt of a compound represented by the following general formula [AI], [A-II], [A-III] or [A-IV] and at least bromide, And a bleaching solution for silver halide color photographic light-sensitive materials having a molar ratio of (bromide ion concentration) / (iron ion concentration) of 2.5 or less.

[0012]

[Chemical 5]

In the formula, A ₁ , A ₂ , A ₃ and A ₄ are each a hydrogen atom, a hydroxyl group, --CH ₂ COOM ₃ , --COOM ₃ , --PO ₃ (M
₃ ) ₂ , —CH ₂ OH or a lower alkyl group, which may be the same or different. However, at least one of A ₁ , A ₂ , A ₃ and A ₄ is —CH ₂ COOM ₃ , —COOM ₃ or —PO ₃ (M ₃ ) ₂
Is. M ₁ , M ₂ and M ₃ each represent a hydrogen atom, an alkali metal atom, an ammonium group or an organic ammonium group.

[0014]

[Chemical 6]

In the formula, A ₅ , A ₆ , A ₇ and A ₈ are each --CH
₂ OH, —PO ₃ (M ₄ ) ₂ or —COOM ₄ are shown, and they may be the same or different. M ₄ is a hydrogen atom, an alkali metal atom,
It represents an ammonium group or an organic ammonium group. X ₁ is an alkylene group having 2 to 6 carbon atoms _{- (B 1 O) m1 B} 2 - represents a. m ₁ represents an integer of ₁ to 8, B ₁ and B ₂ each represent an alkylene group having 1 to 5 carbon atoms, and may be the same or different.

[0016]

[Chemical 7]

Where A ₉ , A ₁₀ , A ₁₁ and A ₁₂ are each
It represents —COOM ₅ , —PO ₃ (M ₆ ) ₂ or —CH ₂ OH, which may be the same or different. M ₅ and M ₆ each represent a hydrogen atom, an alkali metal atom, an ammonium group or an organic ammonium group. X ₂ is a linear or branched alkylene group having 2 to 6 carbon atoms, a saturated or unsaturated organic group forming a ring, or-(B
₃ O) _m2 B ₄ - represents a. m ₂ represents an integer of 1 to 8, B ₃ and B ₄ each represent an alkylene group having 1 to 5 carbon atoms, and may be the same or different. n ₁ , n ₂ , n ₃ and n ₄ are each 1
Represents the above integers, which may be the same or different,
At least one is two or more.

[0018]

[Chemical 8]

Where A ₁₃ , A ₁₄ , A ₁₅ and A ₁₆ are each
Represents a -CH ₂ OH, -COOM ₇ or -PO ₃ M ₈ M _9. M ₇ , M ₈ and M ₉ each represent a hydrogen atom, an alkali metal atom, an ammonium group or an organic ammonium group. X ₃ has 3 to 3 carbon atoms
6 represents a substituted or unsubstituted alkylene group.

(2) The bleaching solution for silver halide color photographic light-sensitive materials according to (1), wherein the ammonium ion concentration in the bleaching solution is 50 mol% or less of the total cation concentration.

(3) The ferric complex salt is a compound represented by the general formula [AI]
V] is a ferric complex salt of the compound represented by (1) or (2)
A bleaching solution for the silver halide color photographic light-sensitive material described.

(4) The above general formulas [A-I], [A-II],
Containing at least one ferric complex salt of the compound represented by [A-III] or [A-IV] and bromide, and (molar bromide ion concentration) / (iron ion concentration) is a molar ratio.
A method for processing a silver halide color photographic light-sensitive material using a bleaching solution of 2.5 or less.

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 ₃ , —PO ₃ (M ₃ ) ₂ , —CH ₂ OH or a lower alkyl group (methyl, ethyl, isopropyl, propyl, etc.). ) Represents. However, at least one of A ₁ , A ₂ , A ₃ and A ₄ is —CH ₂ COOM ₃ , —COOM ₃ or —PO ₃ (M ₃ ) ₂ .
M ₁ , M ₂ and M ₃ each represent a hydrogen atom, an alkali metal atom, an ammonium group or an organic ammonium group (eg, trimethylammonium, triethanolammonium group, etc.).

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

[0026]

[Chemical 9]

[0027]

[Chemical 10]

The compounds represented by the above general formula [AI] are disclosed in JP-A-63-267750, JP-A-63-267751 and JP-A-2-115172.
No. 2-295954 and the like. Among these, a particularly preferable compound 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 _{5 to} A ₈ may be the same or different and each is --CH ₂ OH, --PO ₃ (M ₄ ) ₂ or --COO.
Represents M ₄ . M ₄ represents a hydrogen atom, an alkali metal atom (eg sodium, potassium), an ammonium group or an organic ammonium group (eg ammonium, methylammonium, trimethylammonium etc.). X ₁ is a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms or-(B
₁ O) m ₁ B ₂ −. 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. As the alkylene group represented by X ₁ ,
Examples thereof include ethylene, trimethylene and tetramethylene. Further, as the alkylene group represented by B ₁ and B ₂ ,
Methylene, ethylene, trimethylene and the like can be mentioned. X
_As the substituent of the alkylene group represented by ₁ , B ₁ or B ₂ ,
Examples thereof include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms (eg, methyl, ethyl, etc.). m ₁ represents an integer of ₁ to 8, preferably 1 to 4.

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

[0032]

[Chemical 11]

[0033]

[Chemical 12]

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) and (A-
II-3) and (A-II-14).

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

In the formula, A _{9 to} A ₁₂ may be the same or different and each represents --CH ₂ OH, --PO ₃ (M ₆ ) ₂ or --COOM ₅ . M ₅ and M ₆ are a hydrogen atom, an alkali metal atom (eg sodium, potassium), an ammonium group or an organic ammonium group (eg ammonium, methylammonium,
Trimethylammonium and the like).

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

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

[0039]

[Chemical 13]

[0040]

[Chemical 14]

[0041]

[Chemical 15]

[0042]

[Chemical 16]

The above (A-III-16) and (A-III-1)
7), (A-III-18), (A-III-19), (A-III-
20) includes both trans and 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 compound represented by formula (A-IV) is described in detail below.

In the formula, A _{13 to} A ₁₆ are Japanese Patent Application No. 1-260628, page 12
Since it has the same meaning as A _{1 to} A ₄ described in lines 15 to 3, page 15, detailed description thereof will be omitted.

M ₇ , M ₈ and M ₉ are M of the general formula [A-III].
₅ , the atom or group explained in M ₆ , and X ₃ is represented by the general formula [AI
The same groups as those described for X ₂ in II] can be mentioned.

Preferred specific examples of the compound represented by the above general formula [A-IV] are shown below.

[0050]

[Chemical 17]

As the ferric complex salt of these compounds (A-IV-1) to (A-IV-12), any of sodium salt, potassium salt and ammonium salt of these ferric complex salts may be optionally used. it can. From the viewpoint of the effect and solubility of the object of the present invention, potassium salts of these ferric complex salts are preferably used.

Among the above specific examples, those particularly preferably used are (A-IV-1), (A-IV-3) and (A-IV-
4), (A-IV-5) and (A-IV-9), and particularly preferred is (A-IV-1).

The addition amount of the ferric complex salt of the compound represented by the above general formulas [AI] to [A-IV] is preferably 0.1 to 2.0 mol per liter of the bleaching solution, more preferably 0.
It is 15 to 1.5 mol.

In the present invention, as the bleaching agent, in addition to the iron complex salts of the compounds represented by the above general formulas [AI] to [A-IV], the ferric complex salts of the following compounds can be used in the bleaching solution. ..

[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] nitrilotrispropion Acid [A'-15] triethylenetetramine hexaacetic acid A'-16] ethylenediaminetetrakispropionic acid [A'-17] 1,3-propylenediaminetetraacetic acid [A'-18] glycol etherdiaminetetraacetic acid Among the above, preferred are [AI] and [A]. −
IV] is a bleaching solution using a ferric complex salt, and the most preferred is a bleaching solution using a ferric complex salt of [A-IV].

According to the present invention, the halogen ion concentration [molar
/ l]) / (iron ion concentration [mol / l]) is 2.5 or less, more preferably 0.2 to 2.1, and most preferably 0.8 to 1.7.

As the halogen ion, bromide ion, chloride ion and iodide ion are used, but bromide ion is preferable in order to exert the effects of the present invention most effectively.

The bromide ion generally includes sodium bromide, potassium bromide, ammonium bromide, lithium bromide and the like. However, in order to exert the effect of the present invention more effectively, potassium bromide and ammonium bromide are used. Preferably, potassium bromide is preferable for the most effective display.

The ammonium ion concentration is preferably 50 mol% or less, more preferably 30 mol% or less, and most preferably 10 mol% or less, based on the total concentration of cations added to the bleaching solution.

The temperature of the bleaching 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 to 5.5. In addition, p of bleaching solution
H is the pH of the processing tank at the time of processing the light-sensitive material and can be clearly distinguished from the pH of the so-called replenisher.

In addition to the above, the bleaching solution of the present invention may contain a bleaching accelerator. Particularly preferred bleaching accelerators are (B-1) to (B-23) listed below.

[0063]

[Chemical 18]

[0064]

[Chemical 19]

The replenishing amount of the bleaching solution is preferably 500 ml or less per 1 m ² of the color light-sensitive material, more preferably ²⁰ ml-400.
ml, most preferably 40 ml to 350 ml, and the lower the replenishment amount, the more remarkable the effect of the present invention.

In the present invention, in order to enhance the activity of the bleaching solution, air or oxygen may be blown in the treatment bath and the treatment replenisher storage tank, if desired.
Alternatively, a suitable oxidizing agent such as hydrogen peroxide, bromate, persulfate or the like may be added appropriately.

As the fixing agent used in the fixing solution in 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, more preferably 0.5 mol / l when processing a color negative film.
It is 1 or more.

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 fixer or bleach-fixer according to the present invention comprises
In addition to these fixing agents, a pH buffering agent composed of various salts may be used alone or in combination of two or more kinds.

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.

The treatment time with the bleaching solution of the present invention 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 20.
It is in the range of seconds. The processing time with the bleach-fixing solution is preferably 4 minutes or less, more preferably 10 seconds to 2 minutes 20 seconds.

In the present invention, it is preferable as an embodiment of the present invention to apply forced liquid agitation to the bleaching solution. The reason is that not only the effects of the object of the present invention are better exhibited, but also rapid processing suitability is obtained. Here, the forced liquid stirring means not a normal stirring movement of the liquid but a forced stirring by adding a stirring means. 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, the crossover time from the color developing tank to the bleaching tank is preferably within 10 seconds,
More preferably, when it is within 7 seconds, it is effective against bleaching fog, which is an effect different from the present invention.

The bleaching solution according to the present invention preferably contains substantially no acetic acid from the viewpoint of the effect of the present invention.

The bleaching solution according to the present invention preferably contains a compound represented by the following general formula [II].

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

In the general formula [II], the n-valent organic group represented by A is an alkylene group (eg methylene, ethylene, trimethylene, tetramethylene, etc.), an alkenylene group (eg ethenylene), an alkynylene group (eg ethinylene). ), A cycloalkylene group (eg 1,4-cyclohexanediyl), an arylene group (eg o-phenylene, p-phenylene etc.), an alkanetriyl group (eg 1,
2,3-propanetriyl), an arylenetriyl group (for example, 1,2,4-benzenetriyl) and the like.

The n-valent group represented by A described above includes those having a substituent (eg, hydroxyl group, alkyl group, halogen atom, etc.) (eg, 1,2-dihydroxyethylene, hydroxyethylene, 2-hydroxy). -1,2,3-propanetriyl, methyl-p-phenylene, 1-hydroxy-2-chloroethylene, chloromethylene, chloroethenylene, etc.).

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

[0080]

[Chemical 20]

[0081]

[Chemical 21]

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, and more preferably 0.2 to 1.0 mol, per liter of the treatment liquid.

Next, the color photographic light-sensitive material to which the bleaching 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 films, those for color paper and those for color reversal. As the silver halide grains for color negative films, 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 preferred. Among them, the average silver iodide content of the present invention is preferably 5 to 12 mol%, most preferably 8 to 11 mol%.

In the light-sensitive material for color negative films used in the present invention, the silver halide emulsions 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 I- Item B Non-uniform 〃 Halogen conversion 994 I-C item 〃 Substitution 〃 Metal-containing 994 I-D item Monodisperse 995 I-F item Solvent addition 〃 Latent image formation surface 995 I-G item Internal 〃 Applied sensitizer Negative 995 Item I-H Positive (including internal fog grains) 〃 Mix and use emulsion 995 Item I-J Desalting item 995 II-A In the present invention, the silver halide emulsion is subjected to physical ripening, chemical ripening and spectral sensitization. Use what you have done. Additives used in such a process are described in Research Disclosure Nos. 17643, No. 18716 and No. 308119 (hereinafter abbreviated as RD17643, RD18716 and RD308119, respectively).

The description is given below.

[Items] [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. Below are the relevant locations.

[Items] [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. Below are the relevant locations.

[Item] [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 above-mentioned 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 the above-mentioned RD308119.
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 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,
More preferably, those containing 95 mol% or more, and most preferably those containing 99 mol% or more are used.

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, 1 mol% or less is preferable, more preferably 0.5 mol% or less, and most preferably zero. Is. The silver halide grains mainly composed of silver chloride containing 50 mol% or more of silver chloride may be applied to at least one silver halide emulsion layer, but preferably to all light-sensitive silver halide emulsion layers. It is applied.

The crystal of the silver halide grains may be normal crystal, twin crystal or other crystal, 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 have a layer (phase) -like structure (core / shell type) in which the inside and the outside are different. Good. Further, these silver halides may be of a type that forms a latent image mainly on the surface or a type that forms inside of grains. Further, tabular silver halide grains (JP-A-58-113934 and 61-47)
No. 959) can also be used. In addition, JP-A-64-2683
The silver halides described in No. 7, No. 64-26838, No. 64-77047, etc. can be used.

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

Further, for example, seed particles are prepared by an acidic method, and further,
It may be a method of growing by an ammonia method having a high growth rate to a predetermined size. When growing silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled so that the amount of silver ions corresponding to the growth rate of silver halide grains as described in, for example, JP-A-54-48521. 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.
Pyrazolone couplers and pyrazolotriazoles 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.

The color coupler can be, for example, a 6, 4 or 2 equivalent coupler, but in the present invention a 2 equivalent coupler is especially preferred.

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) W.Pelz's “Farbkuppler”; K. Venkataraman, “The Chemirsry of Synthetic Soy”
Dyes), Vol. 4, 341-387, Academic Press (Ac
ademic Press), "The Theory of the Photograp"
hic Process), 4th Edition, pages 353-362; and Research Disclosure No. 17643, Section VII.

In the present invention, in particular, JP-A-63-106 is used.
No. 1 described in JP-A No. 63-106655, pages 29 to 34 as magenta couplers represented by the general formula [M-1] as described on page 26 of 655.
To No. 77), and cyan couplers represented by the general formula [C-I] or [C-II] also described on page 34 (specifically exemplified cyan couplers are the same as those described in 37).
(C'-1) to (C'-82) and (C "-described on page 42)
1) to (C ″ -36)), and high speed yellow couplers also described on page 20 (specifically exemplified yellow couplers, (Y′-) on pages 21 to 26 of the same specification).
1) to (Y'-39) are preferable from the viewpoint of the effect of the present invention.

In order to achieve the object of the present invention more effectively, the color photographic material according to the present invention can be prepared by using the following general formula [M
It is preferable to use a magenta coupler represented by -I].

[0106]

[Chemical formula 22]

In the formula, Z 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 general formula [MI], the substituent represented by R is not particularly limited, but is 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 residue, etc. are also mentioned.

The substituent represented by R, the group represented by X which can be removed 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 formula [MI] are the same as those described in EP 0327272, page 5, line 23 to page 8, line 52.

Typical examples of magenta couplers represented by the general formula [MI] are shown below.

[0111]

[Chemical formula 23]

[0112]

[Chemical formula 24]

[0113]

[Chemical 25]

In addition to the above typical examples, specific examples of the compound according to the present invention include compounds described in Japanese Patent Application No. 2-218720, pp. 63-82, No. 13, 34, 42,57 ~ 59,61,6
Compounds represented by 2,65 to 67, European Published Patent No. 0327272 10
~ No. 3, 5-2 among the compounds described on page 28
0,22-33,35-60,62-77 and the same 023
No. 1 among the compounds described in No. 5913 on pages 36 to 92
~ 4, 6, 8-17, 19-24, 26-43, 45-59, 61-10
4, 106-121, 123-162, 164-223 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.

[0116] 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 bleaching solution is mixed in a color developing solution. Since it has another effect of making the influence on the photographic performance that occurs at the time extremely small, it can be mentioned as a more preferable embodiment in the present invention.

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

The silver halide emulsions can be prepared by conventional methods, such as single or double inflow with constant or accelerated rush of material. Especially preferred is the double inflow preparation method with controlled pAg; Research Disclosure N
See o.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. Ring formers can also be used as chemical sensitizers, for example silver compounds such as those described in Belgian Patents 493,464 and 568,687, and polyamines such as diethylenetriamine or aminomethyl sulfonic acids according to Belgian Patent 547,323. It is a derivative. Money,
Noble metals and noble metal compounds such as platinum, palladium, iridium, ruthenium or rhodium are also suitable sensitizers. This chemical sensitization method is based on Zeitschrift Fair Bissenscherich Photography (Z.Wis
s.Photo.) 46 , 65-72 (1951) in R. Kosiovsky's paper; and Research Disclosure No. 17643, Section III above.
See also

The 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 Research Disclosure No. 17643, section IV above.
reference.

For the emulsion mainly containing silver chloride, conventional antifoggants and stabilizers can be used. Azaindenes are particularly suitable stabilizers, preferably tetra- and penta-azaindenes, especially those substituted with hydroxyl or amino groups. Compounds of this type are, for example, the Birr article, Zeitschrift-Für-Bissen-Schagliche Photography (Z.Wiss.Photo.) 4
7,1952, pp. 2-58, and Research Disclosure No. 17643, above, 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; eg DE-A 2,044,922, US Pat. Nos. 3,370,952 and 4,080,21.
See No. 1.

The support for the color light-sensitive material used in the present invention is, for example, baryta paper, polyethylene-coated paper,
Polypropylene synthetic paper, a transparent support provided with a reflective layer or in combination with a reflector, for example, a glass plate, cellulose acetate, cellulose nitrate, or a polyester film such as polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film and the like. Alternatively, it may be a usual transparent support.

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, motion picture color films, color films for televisions, etc. which are used for general use or for movies. It can be applied to photosensitive materials.

[0126]

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 In the following examples, the addition amount in the 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) One side (surface) of a triacetyl cellulose film support (75 μm) is subjected to undercoating, and then the support is sandwiched between the surface and the undercoated surface. On the opposite surface (back surface), each layer having the composition shown below was sequentially formed from the support side.

Back side first layer Alumina sol AS-100 (aluminum oxide) (manufactured by Nissan Chemical Industries, Ltd.) 0.8 g Back side second layer diacetyl cellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle size 0.2 μm) 50 mg Then, undercoating On the surface of the obtained triacetyl cellulose film support, each layer having the composition shown below was 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 0.15 g UV absorber (UV-1) 0.20 g Colored cyan coupler (CC-1) 0.02 g High boiling point 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 grain 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) 0.006g 〃 (D-2) 0.01g High boiling point solvent (Oil-1) 0.55g Gelatin 1.0g 4th layer; high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain size 0.7μ m) 0.9 g Sensitizing dye (S-1) 1.7 × 10 ^-4 (mol / silver 1 mol) 〃 (S-2) 1.6 × 10 ^-4 (mol / silver 1 mol) 〃 (S-3) 0.2 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-2) 0.23g Colored cyan coupler (CC-1) 0.03g DIR compound (D-2) 0.02g High boiling solvent (Oil-1) 0.30g Gelatin 1.0 g Fifth layer; intermediate layer (IL-2) gelatin 0.8 g Sixth layer; low-sensitivity green-sensitive emulsion layer (GL) 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) 0.0
2g High boiling point solvent (Oil-2) 0.7
g 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 (mol / silver 1 mol) ) 〃 (S-7) 2.0 × 10 ^-4 (mol / silver 1 mol) 〃 (S-8) 0.5 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (MA) 0.5 g 〃 (M- B) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g 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) 0.07g 〃 (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 ( BH) silver iodobromide emulsion (average particle size 0.3 [mu] m) 0.25 g 〃 (average particle size 0.4 .mu.m) 0.25 g sensitizing dye (S-9) 5.8 × 10 -4 ( mol / mole of silver) yellow coupler (Y 1) 0.71g 〃 (Y-2) 0.30g DIR compound (D-1) 0.003g 〃 (D-2) 0.006g High boiling point solvent (Oil-2) 0.18g Gelatin 1.2g 10th layer; high sensitivity blue sensitivity Emulsion layer (BH) Silver iodobromide emulsion (average grain 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 point solvent (Oil-2) 0.05 g Gelatin 0.9 g 11th layer; 1st protective layer (PRO- 1) Silver iodobromide (average particle size 0.08 μm) 0.3 g Ultraviolet absorber (UV-1) 0.07 g 〃 (UV-2) 0.10 g Additive (HS-1) 0.2 g 〃 (HS-2) 0.1 g High boiling point solvent (Oil-1) 0.07g 〃 (Oil-3) 0.07g Gelatin 0.85g 12th layer; 2nd protective layer (PRO-2) Compound A 0.04g Compound B 0.004g Polymethylmethacrylate (average particle size 3 μm ) 0.02g methylmeth Acrylate: Ethyl methacrylate: Methacrylic acid = 3: 3: 4 (weight ratio) copolymer (average particle size 3 μm) 0.13 g The above 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 (those having 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 ).

[0131]

[Chemical formula 26]

[0132]

[Chemical 27]

[0133]

[Chemical 28]

[0134]

[Chemical 29]

[0135]

[Chemical 30]

[0136]

[Chemical 31]

[0137]

[Chemical 32]

[0138]

[Chemical 33]

[0139]

[Chemical 34]

[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 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 pH 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, while maintaining a flow rate ratio of <H-1> and <S-1> of 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 pAg10.1 and pH6.0.
-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 methanol solution of compound-1 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 103
0.5 ml <S-1> Silver nitrate 309.
2g 28% Aqueous ammonia solution Equivalent to finish with water 1030.5ml <H-2> Ocein gelatin 302.1g Potassium bromide 770.0g Potassium iodide 33.2g Finish with water 3776.8ml <S-2> Silver nitrate 1133.0g 28% Ammonia aqueous solution Equivalent water Finish with 3776.8 ml

[0148]

[Chemical 35]

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 grain 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 light-sensitive material sample thus prepared was subjected to wedge exposure according to a conventional method and then subjected to running processing according to the following processing steps. However, the running treatment was continuously performed until the volume of the bleaching tank was doubled (2R).

Treatment process Treatment time Treatment temperature Replenishment amount (135 size 24EX1 true) (1) Color development (1 tank) 3 minutes 15 seconds 38 ℃ 18ml (2) Bleach (〃) 40 seconds 38 ℃ 2.5ml ( 3) Settling (〃) 1 minute 38 ℃ 20ml (4) Stabilization (3 tank Cascade) 1 minute 38 ℃ 40ml (5) Drying (40-80 ℃) 1 minute Color developer potassium carbonate 30g Sodium hydrogencarbonate 2.5 g 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 developing 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 6.0g Potassium hydroxide 2g Diethylenetriaminepentaacetic acid 3.0g Add water to make 1 liter and adjust to pH 10.20 with potassium hydroxide or 20% sulfuric acid.

Bleaching tank solution Organic acid Ferric complex salt (listed in Table 1) 0.35 mol Ethylenediaminetetraacetic acid 10 g Potassium bromide Listed in Table 1 Maleic acid 50 g Potassium carbonate, adjusted pH to 4.2 with nitric acid, and added water Finish to 1 liter.

Bleaching 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 solution and replenisher) Potassium thiosulfate (70% solution) 350 ml Sodium thiocyanate 20 g Anhydrous sodium bisulfite 12 g Sodium metabisulfite 2.5 g Ethylenediaminetetraacetic acid disodium 0.5 g Water was added to make 1 liter. Adjust to pH 6.0 with acetic acid and aqueous ammonia.

Stabilizing solution (tank solution and replenishing solution) Hexamethylenetetramine 5 g Diethylene glycol 2 g p-Nonylphenol / ethylene oxide 10 mol adduct 2 g Adjust pH to 8.0 with potassium hydroxide, and add water to make 1 liter.

The amount of residual silver after the running treatment and the appearance of the bleaching tank solution (tar generation, crystal precipitation) were visually evaluated.

The results are summarized in Table 1. In addition, XX to ◎ in the table are as follows.

⊚ No precipitation of tar or crystals was observed. ∙ Very slight suspended matter was observed on the liquid surface or tank liquid surface. △ Slight generation was observed on the liquid surface or tank liquid surface. × Liquid surface or tank liquid. Clearly visible on the surface XX Large amount is found on the liquid surface or tank liquid surface

[0162]

[Table 1]

As is clear from Table 1, in the bleaching solution of EDTA.Fe, although the bleaching capacity tends to increase slightly as the (bromide ion concentration) / (iron ion concentration) increases, the precipitation of tar and crystals Occurs. In the bleaching solution using the ferric iron complex salt of the present invention, by controlling (bromide ion concentration) / (iron ion concentration) within a specific range, not only tar generation and crystal precipitation are suppressed but also desilvering property is good. It turned out to be.

Example 2 (Preparation of color photographic light-sensitive material [color paper]) A paper support was coated on one side with polyethylene, and on the other side with a polyethylene oxide containing titanium oxide on the side of the first layer. 2, each layer having the constitution shown in Table 3 was applied to prepare a multilayer color light-sensitive material. The coating liquid was prepared as follows.

First Layer Coating Liquid Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 100 g, (ST-2) 6.67 g, 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.

[0168]

[Table 2]

[0169]

[Table 3]

[0170]

[Chemical 36]

[0171]

[Chemical 37]

[0172]

[Chemical 38]

[0173]

[Chemical Formula 39]

[Preparation Method of 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 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added to 600 ml (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

[0183]

[Chemical 40]

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 37.5 ± 0.5 ° C. 20 seconds 55 ml / m ² (3) Fixing 37.5 ± 0.5 ° C. 20 seconds 55 ml / m ² (4) Stable (3-tank cascade) 30 to 34 ° C 90 seconds 200 ml / m ² (5) Dry 60 to 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 Potassium chloride 2.5 g Diethylenetriamine pentaacetic acid 5 g Potassium sulfite 0.2 g Color developing agent (3-methyl-4-amino-N-ethyl-N- (β-methanesulfone) Amidoethyl) aniline sulfate) 6.0 g Potassium carbonate 25 g Potassium hydrogen carbonate 5 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.10 with potassium hydroxide or sulfuric acid.

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

[Bleaching Solution] Ferric acid complex salt of organic acid (described in Table 4) 0.2 mol Potassium bromide Described in Table 4 Maleic acid 20 g Water was added to make a total amount of 1 liter and used at pH 4.0.

[Bleaching Replenisher] The concentration of each additive in the above bleaching solution was 1.25 times and the pH was 3.0.

[Fixing Solution and Fixing Replenisher] Sodium thiosulfate 30 g Potassium thiosulfate 20 g Sodium sulfite 10 g Potassium thiocyanate 20 g Sodium metabisulfate 1.5 g Water is added to bring the total volume to 1 liter.

[Stabilizer and Replenisher] o-Phenylphenol 0.1 g Ubitex MST (manufactured by Ciba Geigy) 1.0 g Zinc sulfate 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 pH to 7.8 with aqueous ammonia or sulfuric acid, and adjust to 1 liter with water.

A running process was carried out using the color paper and the processing solution thus prepared.

In the running process, the automatic developing machine was filled with the above-mentioned color developing tank solution, and also with the bleaching tank solution, the fixing tank solution and the stabilizing tank solution, and the above-mentioned color developing replenisher solution was added while processing the color paper sample. The bleach-fix replenisher and the stable replenisher were replenished through a metering pump.

The running treatment was carried out continuously while performing aeration until the amount of the bleaching tank solution replenished in the bleaching tank solution became three times the volume of the bleaching tank solution.

After the treatment, the exposure-exposed portion was divided into two, and the amount of residual silver was measured by fluorescent X-ray. Further, the appearance of the bleaching tank liquid (generation of tar) at the end of running was visually evaluated. Furthermore, the precipitation of crystals in the aeration part was observed. The results are shown in Table 4.

XX in the column of tar generation and crystal precipitation in Table 4
The meanings of ⊚ are the same as in Table 1 in Example 1.

[0196]

[Table 4]

As is clear from Table 4, in the bleaching solution using the ferric iron complex salt of the present invention, by setting the (bromide ion concentration) / (iron ion concentration) within the range of the present invention, tar generation It was found that not only the crystal precipitation was suppressed but also the desilvering property was improved.

Example 3 Chelating agents commonly known for use in 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 guideline for chemicals test (adopted May 12, 1981).

As a result, the iron salt of the chelating agent of the present invention has extremely good biodegradability, whereas EDTA and DT
It was found that iron salts of PA and HEDTA were hardly decomposed, and the chelating agent of the present invention was extremely preferable from the standpoint of global environment protection.

Example 4 The magenta coupler (M-C) in the color paper samples used in Experiment Nos. 2-9, 2-14 and 2-19 of Example 2 is exemplified. Magenta couplers (M-5), ( M-8), (M-
11), (M-9), (M-12), (M-13), (M-
7) and (M-4) were replaced by the same experiment, 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 Magenta coupler (M- in the color negative film sample used in Experiment Nos. 1-9, 1-14 and 1-19 of Example 1)
A) and (MB) are illustrated as magenta couplers (M-2),
The same experiment was carried out by replacing (M-6), (M-8), (M-1), (M-10) and (M-3) with a residual silver amount improved by 30 to 35%. The yellow fog density was also improved by 50%.

Example 6 Using the sample of Experiment No. 1-6 of Example 1, the same experiment was conducted by changing the cation ratio in the bleaching solution as shown in Table 5.
However, the amount of bromide added was 0.46 mol / l. ([Bromide ion concentration] / [Iron ion concentration] = 1.3 in this case)
1)

[0203]

[Table 5]

As is clear from Table 5, the lower the ratio of ammonium ion, the more effectively the effect of the present invention is exhibited.

[0205]

According to the present invention, a silver halide color photograph which has a rapid desilvering property even at a low replenishment rate, is free from tar and crystal precipitation even in a long-term continuous processing, and is excellent in biodegradability. A bleaching solution for a light-sensitive material and a method for processing a color light-sensitive material using the same are provided.

Claims (4)

[Claims] 1. The following general formulas [A-I], [A-II],
Containing at least one ferric complex salt of the compound represented by [A-III] or [A-IV] and bromide, and (molar bromide ion concentration) / (iron ion concentration) is a molar ratio.
A bleaching solution for silver halide color photographic light-sensitive materials, which is 2.5 or less. [Chemical 1] [Each _{wherein, A 1, A 2, A} 3 and A ₄ is a hydrogen atom, a hydroxyl _{group, -CH 2 COOM 3, -COOM 3} , -PO 3 (M 3) 2, -CH 2
It represents OH or a lower alkyl group and may be the same or different. However, at least one of A ₁ , A ₂ , A ₃ and A ₄ is —CH ₂ COOM ₃ , —COOM ₃ or —PO ₃ (M ₃ ) ₂ .
M ₁ , M ₂ and M ₃ each represent a hydrogen atom, an alkali metal atom, an ammonium group or an organic ammonium group. ] [Chemical 2] Wherein, A _5, each A _6, A ₇ and A ₈ are, -CH ₂ OH, -PO ₃
(M ₄₎ represents ₂ or -COOM _4, may be the same or different from each other. M ₄ represents a hydrogen atom, an alkali metal atom, an ammonium group or an organic ammonium group. X ₁ has 2 to 2 carbon atoms
6 represents an alkylene group or — (B ₁ O) m ₁ B ₂ —. m ₁ is 1 to
Represents an integer of 8, B ₁ and B ₂ each represent an alkylene group having 1 to 5 carbon atoms, and may be the same or different. ] [Chemical 3] _{Wherein, A 9, A 10, A} 11 and A ₁₂ each, -COOM _5, -
It represents PO ₃ (M ₆ ) ₂ or —CH ₂ OH, which may be the same or different. M ₅ and M ₆ each represent a hydrogen atom, an alkali metal atom, an ammonium group or an organic ammonium group.
X ₂ is a linear or branched alkylene group having 2 to 6 carbon atoms, a saturated or unsaturated organic group forming a ring, or — (B ₃ O) m ₂ B ₄ —
Represents. m ₂ represents an integer of 1 to 8, B ₃ and B ₄ each represent an alkylene group having 1 to 5 carbon atoms, and may be the same or different. Each of n ₁ , n ₂ , n ₃ and n ₄ represents an integer of 1 or more, and may be the same or different, and at least one is 2 or more. ] [Chemical 4] [Wherein A ₁₃ , A ₁₄ , A ₁₅ and A ₁₆ are each —CH ₂ OH,
-COOM ₇ or -PO ₃ M ₈ M ₉ is represented. M ₇ , M ₈ and M ₉ each represent a hydrogen atom, an alkali metal atom, an ammonium group or an organic ammonium group. X ₃ represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms. ] 2. The bleaching solution for a silver halide color photographic light-sensitive material according to claim 1, wherein the ammonium ion concentration in the bleaching solution is 50 mol% or less of the total cation concentration. 3. The ferric complex salt is the compound represented by the general formula [A-IV].
A bleaching solution for a silver halide color photographic light-sensitive material according to claim 1 or 2, which is a ferric complex salt of the compound represented by: 4. The general formulas [AI], [A-II],
Containing at least one ferric complex salt of the compound represented by [A-III] or [A-IV] and bromide, and (molar bromide ion concentration) / (iron ion concentration) is a molar ratio.
A method of processing a silver halide color photographic light-sensitive material, which comprises using a bleaching solution of 2.5 or less.