JPH09160197A - Method for processing silver halide photographic sensitive material and bleach fixing agent to be used for same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the processing agent capable of accelerating bleach fixing processing without causing occurrence of precipitates and having bleaching power by selected of at least one kind of a specified compound and a thiocyanate in the processing agent and operating a process using this processing agent within a specified processing time-length. SOLUTION: This processing agent having a bleaching power is used for the silver halide photographic sensitive material which is processed within a processing time of 1-20sec in the process for using it and this agent contains one of the compounds represented by one of formulae I-III in which Q1 is an atomic group necessary to form a 5- or 6-membered hetero ring; R1 is an alkyl group or the like substituted by a carboxylic acid or its salt; (n) is 1-3; M1 is a cation; Q2 is a 5- or 6-membered mesoionic ring comprising carbon atoms and the like; X is -O -S, N-R2 or the like; R2 is an alkyl group or the like; each of R3 and R4 is an H atom or the like; each of (l1 ) and (l2 ) is 0-10; and each of Y1 and Y2 is an H atom or the like.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a method for processing a silver halide photographic light-sensitive material and a bleach-fixing agent used therefor,
More specifically, it relates to a processing method using a processing agent capable of speeding up the bleach-fixing processing and a bleach-fixing agent.

[0002]

In the field of processing silver halide color photographic light-sensitive materials (hereinafter also referred to as light-sensitive materials), there is an ever-increasing demand for faster processing.

In terms of bleaching, ferric iron complex salts of aminopolycarboxylic acids, which have a high oxidizing power and a low environmental load, are generally used as bleaching agents in bleaching treatment solutions. In the case of bleach-fixing solution, thiosulfate is used as a fixing agent, and this is a factor that is easily oxidized and causes the formation of precipitates. ing. This is an obstacle to making it difficult to speed up the bleach-fixing process.

The present invention has been made in view of the above circumstances, and an object thereof is to accelerate a bleach-fixing process by using a processing agent having a bleaching ability without generation of precipitates.
And to provide such a treating agent.

[0005]

The above object of the present invention comprises at least one compound selected from the compounds represented by the general formulas (1) to (3) and thiocyanates.
A method of processing a silver halide photographic light-sensitive material having a processing step using a processing agent having a bleaching ability, wherein the processing time in the step is 1 second or more and less than 20 seconds, and the processing agent having the bleaching ability is a bleach-fixing agent. The compounds represented by the general formulas (1) to (3) and the thiocyanate are fixing agents, and account for 99.99 mol% or more of all fixing agents containing the fixing agents. , The treatment agent is represented by the general formula (K-1) to (K-
3) containing at least one ferric complex salt of the compound represented by the general formula (K-
1) containing a ferric complex salt of the compound represented by 1), the support of the photosensitive material to be processed is a reflective support, and the processing agent is a compound represented by any of the general formulas (1) to (3) And 0.1 to 3.0 mol / l of a compound selected from thiocyanate, the processing agent containing thiocyanate, and a silver halide photographic light-sensitive material containing substantially no thiosulfate. Bleach-fixing agent for use in the general formula (K-1)
Containing at least one ferric iron complex salt of the compound represented by (K-3), wherein the fixing agent is a ferric iron complex salt of the compound represented by the general formula (K-1) wherein l = 3. The fixing agent contains at least one selected from the compounds represented by the general formulas (1) to (3) and the thiocyanate, and the fixing agent contains the general formulas (1) to ( A step of treating with a bleach-fixing agent, containing 0.1 to 3.0 mol / l of the compound represented by 3) and a compound selected from thiocyanate, and the fixing agent containing thiocyanate. The method of processing a silver halide photographic light-sensitive material having the above, and the processing time of the above step is 1 second or more and less than 20 seconds.

That is, the present inventor has replaced the thiosulfate with a compound selected from the compounds represented by the general formulas (1) to (3) and the thiocyanate (hereinafter also referred to as the fixing agent of the present invention). The inventors of the present invention have found that the use of as a fixing agent can suppress the generation of precipitates and speed up the bleach-fixing process, leading to the present invention.

Further, the compounds represented by the general formulas (1) to (3) having a weakly acidic group such as a carboxyl group also have a function as a buffering agent to reduce bleaching fog and cyan dyes. It was also found to contribute to the improvement of the color restoration performance.

Hereinafter, the present invention will be described in detail for each item.

[Fixing Agent of the Present Invention] The processing agent or bleach-fixing agent having the bleaching ability of the present invention contains substantially no thiosulfate and is represented by the general formulas (1) to (3). And a compound selected from thiocyanate as a fixing agent. The compounds represented by the general formulas (1) to (3) and thiocyanates may be used alone,
Two or more kinds may be used in combination. Hereinafter, general formulas (1) to (3)
The compound represented by will be described.

Specific examples of the compound represented by the general formula (1) include the followings.

[0011]

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[0012]

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These compounds are commercially available from Berichted
er Deutschen Chemischen G
esellschaft 22, 56 (1889), 28, 77 (1895), 29, 2483 (189)
6), Japanese Patent Publication No. 40-28496, and 43-4135.
No. 5, JP-A-50-37436, 50-89034.
No. 51-3231, U.S. Pat. No. 2,271,22
No. 9, No. 2,444,605, No. 2,444,606
Issue 2, Issue 2,444,607, Issue 2,541,924
No. 2,585,388, No. 2,935,404
Issue, Issue 3,060,028, Issue 3,071,465
Issue 3,106,467, Issue 3,137,578
Issue 3,148,066, Issue 3,251,691
Issue 3, Issue 271,154, Issue 3,295,976
Issue No. 3,376,310 Issue 3,420,664
No. 3,420,670, No. 3,511,663
Issue No. 3,598,599 Issue No. 3,615,616
Issue, Journal of Chemical Soc
iety 452,390 (1923), 714,0
00 (1949), Advances in Hete
rocyclic Chemistry 9,165
(1968), Organic Synthesis
IV, 569 (1963), Chemische Ber
It can be synthesized according to the method described in ichte 9,465 (1876).

Next, specific examples of the compound represented by the general formula (2) are shown, but the invention is not limited thereto.

[0015]

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[0016]

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[0017]

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These compounds are Journal of
Heterocyclic Chemistry
2,105 (1965), the same 5,277 (1968),
Journal of Organic Chemis
try 30,567 (1965), the same 322,245
(1967), Journal of Chemica.
l Society 899 (1935), 2,862
5 (1959), ibid. 3,799 (1969), Jour
nal of American Chemical
Society 801, 895 (1958), Che
medical Communication 1,222
(1871), Tetrahedron Letters
1,809 (1967), 5,881 (196)
8), 1,578 (1971), 2,939 (19)
72), JP-A-60-87322, and JP-A-60-1172.
No. 40, No. 60-122936, Berichte
der Deutschen Chemischen G
esellschaft 384, 049 (190
5), Journal of Chemical So
ciency Chemical Communicat
ion 1,224 (1971), Advances
in Heterocyclic Chemistry
19 , 1 (1976), Journal of Ch
electrical Society Perkin Tra
It can be synthesized by the method described in nsaction I 627 (1974) or the like.

In the general formula (3), the lower alkyl group represented by Y ₁ and Y ₂ has a hydrophilic substituent such as a hydroxy group, a carboxyl group, a phosphoric acid group, a sulfuric acid group and an amino group. Alternatively, when l ₁ or l ₂ is 0, at least one of Y ₁ and Y ₂ is a lower alkyl group substituted with a hydrophilic group.

As the compound represented by the general formula (3),
For example, the following are mentioned.

[0021]

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Among the compounds represented by the general formulas (1) to (3), preferred are 1-1, 1-4, 1-8,
1-13, 2-3, 2-4, 2-8, 3-1, 3-5,
3-7, particularly preferably 1-4, 2-3,
It is 3-1.

Examples of thiocyanates that can be used in the present invention include ammonium thiocyanate, sodium thiocyanate and potassium thiocyanate.

In the present invention, it is preferable to mainly use thiocyanate as a processing agent or a bleach-fixing agent having a bleaching ability.

When the processing agent having a bleaching ability is a bleach-fixing agent, the compounds represented by the general formulas (1) to (3) and the thiocyanate are 99.99 mol% of all the fixing agents contained.
In view of the above, it is preferable that the thiosulfate is not substantially contained. The total amount of the compounds represented by the general formulas (1) to (3) and the thiocyanate is preferably 3.0 mol / l or less, more preferably 0.4 to 2.0 mol / l. It is more preferably 0.8 to 1.5 mol / l.

[Bleaching Agent] The processing agent or bleach-fixing agent having a bleaching ability of the present invention comprises a ferric iron complex salt of an aminopolycarboxylic acid compound represented by the general formulas (K-1) to (K-3). It is preferable to contain at least one selected,
Specific examples of the compound are shown below, but the invention is not limited thereto.

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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From the viewpoint of adjusting the pH, the above compound is N
It may be a salt of a, K, NH ₄ , Li or the like, and may be used alone or in combination of two or more kinds. Further, the above compound may contain water of crystallization. The preferred compound is K-
1-25, K-1-26, K-2-1, K-3-2, K
-3-16 is mentioned.

The ferric aminopolycarboxylic acid complex salt is at least 0.10 per liter of the tank solution of the processing solution having a bleaching ability.
It is used in an amount of 0.1 to 0.5 mol, preferably 0.10 to 0.25 mol / l.

The bleach-fixing solution is described in JP-A-3-243948.
It is preferable to add the compound represented by the general formula [FA] or [FB] described in the specification for achieving ammonia-free conversion.

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

In addition to these fixing agents, the processing solution having a bleaching ability may contain pH buffers composed of various salts, either alone or in combination of two or more. 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. In addition, compounds known to be added to a processing solution having a normal bleaching ability, such as alkylamines and polyethylene oxides, can be appropriately added.

The processing solution having a bleaching ability preferably has a pH value.
Used in the range of 1.0 to 8.5, more preferably pH
It is used in the range of 1.5 to 5.0.

The replenishing amount of the processing solution having a bleaching ability of the present invention is preferably 200 ml / m ² or less, more preferably 10 ml / m ^2.
It is 0 ml / m ² or less.

Further, the bleaching treatment liquid preferably contains an organic acid compound represented by the following general formula [A].

General formula [A] 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 (sodium,
Potassium, lithium, etc.) or a hydrogen atom.

In the general formula [A], n represented by A '
Examples of the valent organic group include an alkylene group (methylene group, ethylene group, trimethylene group, tetramethylene group, etc.), alkenylene group (ethenylene group, etc.), alkynylene group (ethynylene group, etc.), cycloalkylene group (1,4-cyclohexane). Diyl group, etc.), arylene group (o-phenylene group, p-phenylene group, etc.), alkanetriyl group (1,
2,3-propanetriyl group) and arenetriyl group (1,2,4-benzenetriyl group).

The n-valent group represented by A'includes those having a substituent (hydroxy group, alkyl group, halogen atom, etc.) (1,2-dihydroxyethylene, hydroxyethylene, 2-hydroxy-group). 1,2,3-propanetriyl, methyl-p-phenylene, 1-hydroxy-2-chloroethylene, chloromethylene, chloroethenylene, etc.). Preferred specific examples of the compound represented by formula [A] are shown below.

[0048]

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[0049]

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Among the above-exemplified compounds, particularly preferable are the exemplified compounds (A-1), (A-3), (A-4),
(A-5), (A-6), (A-13), (A-1
4), (A-15) and (A-20), and particularly preferred are (A-1), (A-5), (A-6) and
(A-13), (A-14), and (A-20).
Examples of the acid salt include ammonium salt, lithium salt, sodium salt, potassium salt and the like, and sodium salt and potassium salt are preferable from the viewpoint of storage stability. These organic acids or salts thereof can be used alone or in combination of two or more kinds.

[Treatment] Preferred specific treatment steps of the treatment method according to the present invention are shown below.

(1) Color development → bleaching → fixing → washing (2) Color developing → bleaching → fixing → washing → stable (3) Coloring development → bleaching → fixing → stable (4) Coloring development → bleaching → fixing → first Stable → Second stability (5) Color development → Bleach → Bleach fixing → Water washing (6) Color development → Bleach → Bleach fixing → Water washing → Stable (7) Color development → Bleach → Bleach fixing → Stable (8) Color development → Bleach ->Bleach-fixing-> 1st stability-> 2nd stability (9) Color development->Bleach-> Bleach fixing->Fixing->Washing-> Stable (10) Color development->Bleach-> Bleach fixing->Fixing-> 1st stability->
Second stability (11) Color development → bleaching → bleach-fixing → water washing (12) Color development → bleaching → bleach-fixing → stability In these steps, (3), (4), (7), (1)
0) and (12) are preferable, and particularly (3), (4) and (1
2) is preferred.

In the present invention, in order to increase the activity of the bleaching solution or the bleach-fixing solution, air or oxygen may be blown in the processing bath and the processing replenisher storage tank, if desired, or a suitable oxidizing agent may be used. For example, hydrogen peroxide, bromate, persulfate or the like may be added as appropriate.

[Color Development] In the present invention, the color developing agent used in the color developing step is preferably a p-phenylenediamine compound having a water-soluble group. Wherein the water-soluble group, p- least one there things listed phenylenediamine amino group of the compound or benzene supranuclear As specific water-soluble group _{- (CH 2) n -CH 2} O
_{H, - (CH 2) m} -NHSO 2 - (CH 2) n CH 3, -
_{(CH 2) m -O- (CH} 2) n -CH 3, - (CH 2 CH 2
O) _n C _m H _{2m + 1} , (m and n each represent an integer of 0 or more.) —COOH group, —SO ₃ H group and the like are preferable.

Examples of specific compounds preferably used in such a color developing agent include the following (C-1) to (C-
18).

[0056]

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[0057]

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[0058]

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Preferred among these compounds are (C
-1), (C-2), (C-3), (C-4), (C-
15), (C-17) and (C-18).

The color developing agent is preferably a hydrochloride,
It is used in the form of sulfate, nitrate and p-toluenesulfonate. The amount of the color developing agent is in the range of 2.5 × 10 ⁻³ mol to 5.5 × 10 ⁻² mol, and preferably 5.0 × 10 ^{−3 to} 4.5 × 10 per 1 l of the color developing solution. ^-2 mol.

In the color developing solution, the following general formula [A],
The inclusion of the organic preservative represented by [B] is preferable for rapid processing and reduction of bluing, and it is also preferable because crystal protrusion on the liquid surface of the color developer tank can be suppressed.

[0062]

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[0063]

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A detailed description of the compound represented by the general formula [A] is described in JP-A-4-67038, and a detailed description of the compound represented by the general formula [B] is described in JP-A-4-21846. It The compound represented by the general formula [A] or [B] is usually used in the form of free amine, hydrochloride, nitrate, oxalate, phosphate, acetate and the like.

The concentration of the compound represented by the general formula [A] or [B] in the color developer and the replenisher is usually 0.2 to 5
It is 0 g / l, preferably 0.5 to 30 g / l, and more preferably 1 to 15 g / l. Further, the compound represented by the general formula [A] or [B] can be used in combination with the conventionally used hydroxylamine and organic preservative, but it is preferable to use no hydroxylamine for development. It is preferable from the viewpoint of sex.

Further, the color developing solution has the following general formula [W],
It is preferable to contain a compound represented by [X], [Y] or [Z].

[0067]

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[In the formula, R ₃₇ represents a hydroxyalkyl group or an aminoalkyl group, and R ₃₈ and R ₃₉ each represent a hydrogen atom, an alkyl group, a hydroxyalkyl group or a benzyl group.
R ₃₇ and R ₃₈ , R ₃₈ and R ₃₉ , R ₃₉ and R ₃₇ or R ₃₇ and R ₃₈
And R ₃₉ may each form a ring. ]

[0069]

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[In the formula, A ′ and B ′ each represent a linear or branched alkylene group, and n and m each represent an integer of 0 to 100. However, both n and m are never 0. In the general formula [W], R ₃₇ represents a hydroxyalkyl group which may be substituted or an aminoalkyl group which may be substituted, and the carbon number of the hydroxyalkyl group and the aminoalkyl group is preferably 1 to 10, and more preferably Is 2
~ 6. Examples of the substituent include a hydroxy group, a carboxy group, a carbonyl group, a sulfo group, a phosphono group, an ammonium group, a nitro group, an amino group and a halogen atom. Examples of R ₃₈ and R ₃₉ include a hydrogen atom, an alkyl group which may have a substituent, and a benzyl group which may have a substituent. A hydrogen atom, a straight chain or branched chain having 1 to 10 carbon atoms An alkyl group which may have a chain substituent is preferable.

As the substituent, a hydroxy group, a carboxy group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, a ureido group, an acyl group, a cyano group, a nitro group, an amino group, a sulfo group, an alkylsulfonyl group, an alkylsulfonylamino group. , An arylsulfonyl group, an arylsulfonylamino group, a phosphono group, a phosphonate residue, and a halogen atom. Preferably a hydroxy group, a carboxyl group, an alkoxycarbonyl group,
It is a carbamoyl group or an amino group, and may be further substituted with a hydroxy group, a carboxy group, a sulfo group or an amino group.

R ₃₇ and R ₃₈ , R ₃₈ and R ₃₉ , R ₃₉ and R ₃₇ or R ₃₇ and R ₃₈ and R ₃₉ may be connected to each other to form a ring.

Preferred specific examples of the compound represented by the above general formula [W] are shown below. The present invention is not limited to these.

(W-1) Ethanolamine (W-2) Diethanolamine (W-3) Triethanolamine (W-4) Di-isopropanolamine (W-5) 2-Methylaminoethanol (W-6) 2- Ethylaminoethanol (W-7) 2-Dimethylaminoethanol (W-8) 2-Diethylaminoethanol (W-9) 1-Diethylamino-2-propanol (W-10) 3-Diethylamino-1-propanol (W-11) ) 3-Dimethylamino-1-propanol (W-12) isopropylaminoethanol (W-13) 3-amino-1-propanol (W-14) 2-amino-2-methyl-1,3-propanediol (W -15) Ethylenediaminetetraisopropanol (W-16) Benzylethanol (W- 7) 2-amino-2- (hydroxymethyl) -
1,3-Propanediol (W-18) 1,3-Diaminopropanol (W-19) 1,3-Bis (2-hydroxyethylmethylamino) -propanol

[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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Of the compounds represented by the general formula [W], particularly preferred are (W-2), (W-3), (W-4) and (W-4).
2).

Preferred specific examples of the compound represented by the above general formula [X] are as follows.

[0082]

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[0083]

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[0084]

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The compounds preferably used in the general formula [X] are (X-1), (X-18) and (X-26).

The amount of the compound represented by the general formula [W] or [X] added is preferably in the range of 1.0 to 100 g / l, more preferably 5.0 to 50 g / l.

[0087]

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[In the formula, at least one of A to F is a sulfonic acid group or a hydroxysulfonyloxy group, or an alkali metal (sodium atom, potassium atom) salt or ammonium salt thereof, and the rest are hydrogen atoms or halogens. Represents either an atom, a saturated or unsaturated alkyl group. ]

[0089]

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[Wherein at least one of G to N is a sulfonic acid group or a hydroxysulfonyloxy group, or an alkali metal (sodium atom, potassium atom) salt or ammonium salt thereof, and the rest are hydrogen atoms or halogens. Represents either an atom, a saturated or unsaturated alkyl group. ] In the general formulas [Y] and [Z], A to F and G to
The saturated or unsaturated alkyl group represented by N preferably has 1 to 10 carbon atoms. The carbon chain may be linear or may have a side chain.

Specific examples of the compound represented by the general formula [Y] or [Z] are shown below, but the invention is not limited thereto.
Although all of the exemplified compounds are shown as sodium salts, some or all of them may be sulfonic acids or hydroxysulfonyloxy compounds.

[0092]

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[0093]

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The addition amount of the compound represented by the general formula [Y] or [Z] is preferably 5 g / l or more, more preferably 10 to 200 g / l.

The color developer replenisher may contain the following developer components in addition to the components described above.

As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate,
Potassium metaborate, trisodium phosphate, tripotassium phosphate, borax and the like can be used alone or in combination within a range where precipitation does not occur and a pH stabilizing effect is maintained. Further, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, borate and the like are used for the necessity of preparation or for the purpose of increasing ionic strength. be able to.

It is preferable that the color developing replenisher contains a fluorescent whitening agent. The fluorescent whitening agent not only improves the white background performance of the unexposed areas of the light-sensitive material, but also provides good results in preventing crystal precipitation.

The fluorescent whitening agent is preferably a triazinyl stilbene type compound, and particularly preferably a compound represented by the following general formula [F].

[0099]

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Detailed description of the compound represented by formula [F] is described in JP-A-4-76038. Further, the triazinyl stilbene-based whitening agent can be synthesized by the usual method described in, for example, “Fluorescent Whitening Agent” (published in August 1976), page 8 edited by Chemical Industry Association. The compound F- exemplified in the above-mentioned publication is preferable as the optical brightener.
4, F-24, F-34, F-35, F-36, F-3
7, F-41. The triazinyl stilbene whitening agent is preferably used in an amount of 0.2 to 10 g, and more preferably 0.4 to 5 g, per liter of color developing replenisher.

Further, a chelating agent represented by the following general formula [L] is preferably added to the color developing replenisher.

[0102]

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A detailed description of the compound represented by the general formula [L] is also given in JP-A-4-76038.

The pH of the color developing solution is preferably 9.5 or more and 13.0 or less, and more preferably 9.8 or more and 12.5 or less. The replenishing amount of the color developing solution is preferably 120 ml / m ² or less, more preferably 20 ml / m ^{2 to} 100.
ml / m ² .

[Fixing and Bleaching Fixing] The fixing agent used in the fixing solution is a compound which reacts with silver halide to form a water-soluble complex salt, for example, thiosulfate such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate. Examples thereof include thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thioureas, thioethers, mesoions and alkylthiosulfonates.

In addition to these fixing agents, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid,
A single pH buffer or two or more pH buffers composed of various salts such as sodium acetate and ammonium hydroxide can be contained. In addition, borate, oxalate, acetate, carbonate, phosphate, etc.
What is known to be added to ordinary fixing solutions and bleach-fixing solutions such as pH buffers, alkylamines and polyethylene oxides can be appropriately added.

The fixing agent is used in an amount of 0.1 mol or more, preferably 0.6 to 4 mol, particularly preferably 0.9 to 3.0 mol, and particularly preferably 1. It is used in the range of 1 to 2.0 mol.

The pH of the fixing solution is preferably in the range of 4-8.

The fixing solution preferably contains a sulfite and a sulfite-releasing compound, and examples of the compound include potassium sulfite, sodium sulfite, ammonium sulfite, ammonium hydrogen sulfite, potassium hydrogen sulfite, sodium hydrogen sulfite, potassium metabisulfite and meta. Examples include sodium bisulfite and ammonium metabisulfite. Furthermore, the compound represented by the following general formula [M-1] or [M-2] is also included.

[0110]

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In the formula, R ¹⁷ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁸ is an optionally substituted alkyl group having 1 to 5 carbon atoms, M ′ is an alkali metal atom, and R ¹⁹ and R ²⁰ are A hydrogen atom or an optionally substituted alkyl group having 1 to 5 carbon atoms, n
₁₀ represents an integer of 0 to 4.

Specific examples of the compound represented by the above general formula will be described below, but the present invention is not limited thereto.

M-1 Formaldehyde Sodium Bisulfite M-2 Acetaldehyde Sodium Bisulfite M-3 Propionaldehyde Sodium Bisulfite M-4 Sodium Butylaldehyde Bisulfite M-5 Succinic Aldehyde Sodium Bisulfite M-6 Glutaraldehyde Bis Bisulfite Sodium M-7 β-Methylglutaraldehyde bis sodium bisulfite M-8 Maleic acid dialdehyde bis sodium bisulfite These sulfites and sulfite-releasing compounds are present in at least 0.1 mol of sulfurous acid per liter of fixer or bleach-fixer. It is preferable that there is 0.12 to 0.55 mol /
The range of 1 is preferable, and the range of 0.15 to 0.50 mol / l is particularly preferable. A range of 0.20 to 0.40 mol / l is particularly preferable. However, the number of moles of these sulfites and sulfite-releasing compounds is shown as a value converted to sulfite.

In carrying out the method of the present invention, silver may be recovered from the processing solution having fixing ability by various methods, and the silver recovery method may be any method as long as silver can be recovered from the processing solution having fixing ability. Any of them may be used, for example, an electrolysis method (see French Patent 2,299,667), a precipitation method (JP-A-52-73037, and German Patents 2,331,22).
No. 0), an ion exchange method (JP-A-51-17114).
No. 2, German Patent No. 2,548,237) and the metal substitution method (see British Patent No. 1,353,805) can be effectively used.

The processing solution having a fixing ability after the recovery of silver is returned to the original processing tank having a fixing ability, and an antioxidant such as sulfite can be added before returning.

[Stabilization] In the present invention, it is preferable to carry out the stabilizing treatment without substantially washing with water subsequent to the bleach-fixing or fixing treatment.

Stabilizers used in the stabilizing treatment include general formulas [CH-I] to [CH-I] described in JP-A-3-243948.
It is preferable to contain a chelating agent represented by [CH-III]. The amount of the chelating agent used was 0.
01-100 g is preferable, and more preferably 0.05-
It is in the range of 50 g, particularly preferably in the range of 0.1 to 20 g.

The stabilizing solution preferably contains a metal salt in combination with the chelating agent. Examples of such metal salts are Ba, Ca, Ce, Co, In, La, Mn, Ni,
There are metal salts of Bi, Pb, Sn, Zn, Ti, Zr, Mg, Al or Sr, and inorganic salts such as halides, hydroxides, sulfates, carbonates, phosphates, acetates or water-soluble chelates. It can be supplied as an agent.

To the stabilizing solution, organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH adjusters (phosphate salts, borate salts, hydrochloric acid, sulfate salts, etc.) are added. can do.

Known antifungal agents can be used alone or in combination.

Further, in the treatment of the present invention, silver may be recovered from the stabilizing solution by a known method.

Further, the stabilizing solution is subjected to ion exchange treatment, electrodialysis treatment (see JP-A-61-28949) and reverse osmosis treatment (JP-A-60-240153 and JP-A-62-25415).
No. 1). It is also preferable to use water which has been previously deionized from water used for the stabilizing solution. That is, the antifungal property of the stabilizer, the stability of the stabilizer, and the image storability are improved. As a means of the deionization treatment, any method may be used as long as the Ca and Mg ions of the washing water after the treatment are reduced to 5 ppm or less. For example, treatment with an ion exchange resin or a reverse osmosis membrane may be used alone or in combination. preferable. The ion exchange resin and the reverse osmosis membrane are described in detail in JP-A-87-1984 and JP-A-89-20511.

No washing treatment is required after the stabilizing treatment, but rinsing, surface washing and the like can be optionally performed by washing with a small amount of water within an extremely short time.

The pH of the stabilizing solution is preferably in the range of 5.5 to 10.0. The pH adjusting agent that can be contained in the stabilizing solution may be any of generally known alkali agents or acid agents.

The treatment temperature for the stabilization treatment is 15 ° C.
The temperature is preferably 70 ° C, more preferably 20 ° C to 55 ° C. The treatment time is preferably 120 seconds or less, more preferably 3 seconds to 90 seconds, and most preferably 6 seconds to 50 seconds.

The replenishing amount of the stabilizing solution is preferably 0.1 to 80 times the carrying-in amount of the pre-bath (fixing solution or bleach-fixing solution) per unit area of the light-sensitive material from the viewpoint of rapid processing property and storability of dye image.
It is particularly preferably 0.5 to 30 times.

The stabilizing tank is preferably composed of a plurality of tanks, preferably 2 to 6 tanks, and particularly preferably 2 to 3 tanks in a counter current system (supplied to the post-bath. It is preferable to adopt a method of overflowing from the previous bath).

[Photosensitive Material] As a silver halide emulsion for a photosensitive material, a silver chloride-based emulsion containing at least 80 mol% of silver chloride is preferably used because of its excellent rapid processing property.

Further, the processing according to the present invention, which has an effect of reducing bleaching fog, is very advantageous for a light-sensitive material for direct viewing using a reflective support.

[0130]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 [Processing Apparatus] FIG. 1 shows an automatic developing machine (hereinafter,
Also called an automatic machine. 2] is a schematic configuration diagram of a main part of FIG. The processing tank of this automatic processor had the structure shown in FIG. In the automatic processor of FIG. 1, the photosensitive material P is exposed and then conveyed by a plurality of pairs of feed rollers, and the developing treatment tank C is conveyed.
First processed in D. After that, the bleach-fixing treatment tank BF and the stabilization tank STB are sequentially conveyed by the roller conveying means and processed. The photosensitive material P which has been subjected to each of these processes is dried in the drying section and discharged outside the machine. The processing using this automatic processor is referred to as processing method 1.

The structure of the processing tank of FIG. 2 is shown below.

In the photosensitive material processing tank 1Y, the lower side of the processing tank tank having a shape along the transport path is defined, and the lower member 13Y also serves as a transport guide for the silver halide photographic photosensitive material. On the transport path between the upper member 12Y, which defines the shape of the upper side of the processing tank along the transport path and also serves as a transport guide for the silver halide photographic light-sensitive material, and the lower member 13Y and the upper member 12Y. It has conveying rollers 16Y, 17Y, and 18Y for driving the silver halide photographic light-sensitive material and conveying the silver halide photographic light-sensitive material. And
Only the insertion port 14Y and the discharge port 15Y of the transport path defined between the lower member 13Y and the upper member 12Y are gas-liquid interfaces of the processing liquid in the processing tank 1Y. Further, although not shown, a transition guide 28Y provided in close contact with the upper member 13Y on the downstream side of the delivery path of the discharge port 15Y and a counter roller for delivering the silver halide photographic light-sensitive material along the transition guide 28Y. A crossing roller pair 30Y is provided.

On the side of the photosensitive material processing tank 1Y, the processing tank 1 is provided.
It has an auxiliary tank 2Y provided separately from Y. Then, a circulation pipe 21Y is formed from the processing tank 1Y to the lower part of the auxiliary tank 2Y so that the processing liquid can flow.

The rod-shaped heater 26Y is arranged so as to penetrate the upper wall of the auxiliary tank 2Y and be immersed in the processing liquid in the auxiliary tank 2Y. The heater 26Y is connected to a processing liquid circulation path and a processing tank 1 based on a temperature detected by a thermometer (not shown) provided in the auxiliary tank 2Y.
The processing solution in Y is heated, in other words, the processing solution in the processing tank 1Y is heated to a temperature range suitable for processing (for example, 20 ° C.).
To 55 ° C.).

The plate-shaped filter 22Y is the auxiliary tank 2
Y and a circulation pipe 29Y to the processing liquid storage tank 4Y
The auxiliary tank 2Y is provided so as to be replaceable, and has a function of removing insolubles, for example, precipitates and the like in the processing liquid. The circulation pipe 29Y communicates with the lower part of the auxiliary tank 2Y and the upper part of the processing liquid storage tank 4Y. The lower part of the processing liquid storage tank 4Y is connected to the suction side of a circulation pump 24Y (circulation means) via a circulation pipe 23Y provided through the lower wall of the processing liquid storage tank 4Y.

The circulation system is the auxiliary tank 2Y / circulation pipe 2
The processing tank 1Y includes the processing liquid circulation path formed by 9Y, the processing liquid storage tank 4Y, the circulation pipe 23Y, the circulation pump 24Y, and the circulation pipe 25Y. The other end of the circulation pipe 25Y communicating with the discharge side of the circulation pump 24Y penetrates the lower wall of the processing tank 1Y, and is connected to a nozzle 27Y that uniformly discharges the processing liquid in the width direction toward the transport path of the processing tank 1Y. Communicating. With such a configuration, when the circulation pump 24Y is operated, the processing liquid is sucked from the auxiliary tank 2Y, discharged to the processing tank 1Y, and again circulated into the auxiliary tank 2Y.

In this embodiment, the volume V _{w of the} processing liquid contained in the processing tank 1Y for processing the photosensitive material is 0.5.
and the volume V _{f of the} processing liquid in the circulation path is 2.5 l
The circulating flow rate V _c of the processing liquid generated by the circulation pump 24Y is 5 l / min, and the total inflow cross-sectional area S _t of the circulating inlet of the processing liquid is 4.25 cm ² .

Using the automatic processor shown in FIG. 1, wedge exposed QA-A6 color paper manufactured by Konica Corp. according to a conventional method was continuously treated at 10 m ² per day for 2 weeks according to the following treatment step (1). .

Processing step (1) Temperature (° C.) Processing time Replenishment amount (ml / m ² ) (1) Color development 39.5 25 seconds 80 (2) Bleach-fixing 38.0 12 seconds 54 (3) Stable * 38 0.030 seconds × 3 180 (4) Drying 60 to 80 30 seconds- * The stabilizing tank was composed of 3 tanks, and the counter current method was used for the previous tank, and the replenishment was performed for the final tank.

[Color-developing tank liquid and replenisher] to 1 liter Color-developing tank liquid replenisher Diethylene glycol 10 g 15 g Sodium p-toluenesulfonate 20 g 30 g Potassium bromide 3.0 × 10 ^-4 mol 1.5 × 10 ^-4 Mole potassium chloride 4.0 × 10 ⁻² mole-color developing agent (C-1) 1.9 × 10 ⁻² mole 2.5 × 10 ⁻³ mole diethylhydroxylamine 3.5 g 5.0 g potassium carbonate 30 g 30 g diethylenetriamine Pentaacetic acid 1.0 g 1.0 g Optical brightener F 1.5 g 1.5 g pH 10.10 10.60

[0142]

Embedded image

[Bleaching and fixing tank liquid and replenishing liquid] to 1 liter Bleaching and fixing tank liquid Replenishing liquid Ammonium salt of ferric complex salt of chelating agent shown in Table 1 0.15 mol 0.30 mol Chelate shown in Table 1 Agent 2.0 g 4.0 g Additive (listed in Table 1) Listed in Table 1 Listed in Table 1 pH 4.00 3.60 [Stable tank liquid and stable replenisher] ~ 1 liter Stabilized tank liquid and replenisher Orthophenyl phenol 0.15g ZnSO ₄ · 7H ₂ O 0.2g ammonium sulfite (40%) 5.0 ml 1-hydroxyethylidene-1,1-diphosphonic acid (60% solution) 3.8 g ethylenediaminetetraacetic acid 2.0g fluorescent brightening Agent (Tinopearl SFP Ciba Geigy) 2.0 g pH 7.80 Using the automatic processor shown in FIG. 1, the type and amount of additives in the bleach-fixing tank solution, ferric complex salt The type of chelating agent that forms
Continuous treatment was performed by changing the treatment time as shown in Table 1.

<Evaluation of bleaching property> At the end of continuous processing, an unexposed color paper sample and a full-exposure color paper sample were processed, and after the processing, 100% by using an infrared densitometer.
The reflection density at 0 nm was measured, and the bleaching property was evaluated by the value obtained by the following formula.

Bleachability = Reflection density of exposed sample on whole surface−
Reflection Density of Unexposed Sample << Amount of Residual Silver >> The amount of residual silver in the sample in the exposed area was measured by the fluorescent X-ray method.

<< Dye Dyeing >> 44 of unexposed samples which have been treated
The spectral reflection density D _min (Y) at 0 nm was measured.

<Odor> The bleach-fix solution was evaluated for the presence or absence of odor.

The above results are shown in Table 1.

[0149]

[Table 1]

NCSA: Ammonium thiocyanate TSA: Ammonium thiosulfate SS: Sodium sulfite According to Table 1, when the fixing agent of the present invention is used in the bleach-fixing solution, the bleaching performance and the fixing performance are excellent even if the bleach-fixing process is accelerated. Also, it can be seen that the colorant is well removed and the generation of odor is suppressed. Further, when a chelating agent represented by the general formula (K-1) and 1 = 3 is used, a remarkable effect is obtained, thiocyanates are excellent in fixing performance, and treatment in less than 20 seconds is possible. It can be seen that it is advantageous for preventing dye dyeing.

Example 2 K-1-26 was used as the chelating agent for the bleach-fixing solution, the type of additive and the amount of the tank solution added were changed as shown in Table 2, and the bleach-fixing treatment time was 17 times. Continuous processing was performed in the same manner as in Example 1 except that the time was set to 2 seconds, and the residual silver amount was measured. The state of the bleach-fixing treatment tank after continuous treatment was observed and evaluated according to the following criteria.

⊚: There is no precipitate ◯: Precipitate is slightly seen on the surface of the treatment liquid, but there is no problem. ×: Precipitate is seen xx: Precipitate is considerably generated. The odor of the bleach-fixing tank after continuous processing was evaluated according to the following criteria.

⊚: No odor ○: Slight odor, but no problem level ×: Odor is felt XX: Significant odor is generated. Table 2 shows the results.

[0154]

[Table 2]

From this, it is understood that in the rapid processing, it is advantageous to use a system containing 99.99 mol% or more of the fixing agent of the present invention, that is, a system containing substantially no thiosulfate.

Example 3 Continuous processing was carried out in the same manner as in Example 2 except that ammonium thiocyanate (NCSA) was used as a fixing agent for the bleach-fixing solution and the tank solution concentration was changed as shown in Table 3. The amount of residual silver was measured. Furthermore, the following evaluation was performed.

<< Bleaching Fog >> The spectral reflection density D _min (C) of the unexposed area at 660 nm was measured and used as a measure of bleaching fog.

<< Color Restoration >> 66 of the whole exposed sample which has been processed
The concentration D ₁ of 0 nm was measured, and this sample was further added with an ethylenediaminetetraammonium iron acetate aqueous solution (30 g / l, pH
After immersing in (7.0, 40 ° C.) for 4 minutes, the concentration D ₂ of 660 nm is measured again at the same portion as the measurement of D ₁ , and ΔD =
It was evaluated at D ₂ -D _1.

The results are shown in Table 3.

[0160]

[Table 3]

Embodiment 4 FIG. 3 is a schematic configuration diagram of a main part of an automatic developing machine used in this embodiment. The processing tank of this automatic processor had the structure shown in FIG. In the automatic developing machine of FIG. 3, the photosensitive material P is exposed and then conveyed by a plurality of pairs of feed rollers and first processed in the development processing tank CD. After that, the bleaching treatment tank BL, the fixing treatment tank Fix, and the stabilization tank STB are sequentially conveyed by the roller conveying means and processed. The photosensitive material P which has been subjected to each of these processes is dried in the drying section and discharged outside the machine. The conditions such as the circulation of the treatment liquid are the same as those in Example 1.
And the same.

Processing performed using the automatic processor of FIG. 3 under the following conditions is referred to as processing method 2.

The processing steps are shown below.

Treatment step (2) Treatment time Treatment temperature Color development 2 minutes 30 seconds 38.0 ° C. Bleach 18 seconds 38.0 ° C. Settling 30 seconds 38.0 ° C. Stability 30 seconds 38.0 ° C. Dry 80 seconds As a light-sensitive material to be processed at 55.0 ° C., QA-A6 paper (light-sensitive material 1) manufactured by Konica Corp. and Konica Color Super DD film (light-sensitive material 2) which were imagewise exposed were used.

[Treatment Solution Formulation: Per 1 L] << Color Developer-1 >> Color developer tank solution described in Example 1 << Color Developer-2 >> Sodium sulfite 3.0 g Diethylenetriamine pentaacetic acid 5 sodium 2.0 g p- Sodium toluene sulfonate 6.0 g Hydroxylamine sulfate 3.0 g Potassium bromide 1.5 g Bis (sulfoethyl) hydroxylamine disodium 2.0 g Potassium carbonate 33.0 g Potassium hydrogen carbonate 3.6 g Potassium iodide 3.0 mg 4-amino -3-Methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulphate (CD-4) 5.0 g Adjust pH to 10.0 with potassium hydroxide or sulfuric acid.

<< Bleaching Solution >> Propanediamine tetraacetic acid ferric ammonium salt As described in Table 4, Propanediamine tetraacetic acid 2.0 g Ammonium bromide 30.0 g Succinic acid 50.0 g Potassium bicarbonate 20.0 g Ammonium thiocyanate Description pH 4.0 << Fixing solution >> Ammonium thiosulfate Described in Table 4 Sodium sulfite 20 g Propanediamine tetraacetic acid 2.0 g << Stabilizing solution-1 >> Stabilizing tank solution described in Example 1 << Stabilizing solution-2 >> m-hydroxybenzaldehyde 2.0 g Ethylenediaminetetraacetic acid ・ 4 sodium 0.05 g << Bleach-fixing solution-2 >> Propanediaminetetraacetic acid ferric ammonium salt Table 4 Propanediaminetetraacetic acid 2.0 g Succinic acid 20 g Ammonium thiocyanate Table 4 According to the processing method 1 or 2, the above-mentioned exposure was conducted under the conditions shown in Table 4. Charge processes were evaluated bleaching and residual silver amount in the same manner as in Example 1. The processing time in the bleach-fixing step was 18 seconds. Table 4 shows the results.

[0167]

[Table 4]

[0168]

According to the present invention, a bleach-fixing treatment can be speeded up, and a processing agent having a bleaching ability without the problem of deposit formation can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of a main part of an automatic developing machine used in an embodiment.

FIG. 2 is a diagram showing a configuration of a processing tank of the automatic processor of FIG.

FIG. 3 is a schematic configuration diagram of a main part of another automatic developing machine used in the embodiment.

[Explanation of Codes] 1Y Processing Tank 2Y Auxiliary Tank 4Y Processing Liquid Storage Tank 12Y Upper Member 13Y Lower Member 16Y Transport Roller 24Y Circulation Pump 25Y Circulation Pipe 27Y Nozzle for Discharging Processing Liquid 28Y Crossover Guide

Claims (16)

[Claims] 1. A process comprising a treatment agent having a bleaching ability, which comprises at least one compound selected from the compounds represented by the following general formulas (1) to (3) and thiocyanate: The processing time of the silver halide photographic light-sensitive material is 1 second or more and less than 20 seconds. Embedded image [In the formula, Q ₁ represents an atomic group necessary for forming a 5- or 6-membered heterocycle, and the formed heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring. R ₁ is an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a hetero group substituted with at least one selected from a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an amino group, or an ammonium salt. Represents a ring group or a single bond. n represents 1 to 3 and M ₁ represents a cation group. [Chemical formula 2] [In the formula, Q ₂ represents a 5- or 6-membered mesoionic ring composed of an atomic group selected from a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a selenium atom, and X represents —O ⁻ , —S ^−.
Or -N ^- represents R _2, R ₂ represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group. ] [Chemical 3] [In the formula, R ₃ and R ₄ are each a hydrogen atom, a hydroxy group,
Represents a carboxyl group, a phosphoric acid group, a sulfuric acid group, an amino group or an alkyl group which may have a substituent, and l ₁ and l ₂ are 0 to
Represents 10. Y ₁ and Y ₂ each represent a hydrogen atom, an alkali metal, a lower alkyl group, or an ammonium group. When l ₁ or l ₂ is 0, at least one of Y ₁ and Y ₂ is substituted with a hydrophilic group. It is a lower alkyl group. ] 2. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the processing agent having a bleaching ability is a bleach-fixing agent. 3. The compounds represented by the general formulas (1) to (3) and thiocyanate are fixing agents, and account for 99.99 mol% or more of all fixing agents containing the fixing agent. 3. The method for processing a silver halide photographic light-sensitive material according to claim 2, wherein 4. The treatment agent is represented by the following general formula (K-1):
4. The method for processing a silver halide photographic light-sensitive material according to claim 1, 2 or 3, which contains at least one ferric complex salt of the compound represented by (K-3). Embedded image [In the formula, A _{1 to} A ₄ are each a hydrogen atom, a hydroxy group,
_{COOZ, -PO 3 (Z 1)} 2, -CH 2 COOZ 2, -C
H ₂ OH or a lower alkyl group which may have a substituent, Z, Z ₁ and Z ₂ are each a hydrogen atom, an ammonium group,
Represents an alkali metal or organic ammonium group, A ₁ ~
At least one of A ₄ is —COOZ, —PO ₃ (Z ₁ ) ₂ ,
It is a -CH ₂ COOZ _2. R ₅ and R ₆ each represent a hydrogen atom or a lower alkyl group which may have a substituent, and adjacent groups may form a ring. k _{1 to} k ₄ and l each represent 1 to 4. These may constitute stereoisomers. [Chemical formula 5] Wherein, A ₁₁ to A ₁₄ are each, -CH ₂ OH, -COOZ ₃
Or —PO ₃ (Z ₄ ) ₂ and each of Z ₃ and Z ₄ represents a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. W is an alkylene group having 2 to 6 carbon atoms or-
_{(B 1 O) m -B 2} - represents, each B ₁ and B ₂ represents an alkylene group having 1 to 5 carbon atoms, m represents 1-8. ] [Chemical 6] [In the formula, A _{21 to} A ₂₄ may be the same or different and each represents a hydrogen atom, a hydroxy group, —COOM ′, or —PO.
₃ (M ₂₁ ) ₂ , —CH ₂ COOM ₂₂ , —CH ₂ OH or a lower alkyl group which may have a substituent. However, A ₂₁ ~
At least one of A ₂₄ is -COOM ', -PO
₃ (M ₂₁ ) ₂ and —CH ₂ COOM ₂₂ . M ₂₁ , M ₂₂ ,
Each M'represents a hydrogen atom, an ammonium group, an alkali metal or an organic ammonium group. ] 5. The general formula (K−) in which the treating agent is 1 = 3.
The method for processing a silver halide photographic light-sensitive material according to claim 4, further comprising a ferric complex salt of the compound represented by 1). 6. The method for processing a silver halide photographic light-sensitive material according to claim 1, 2, 3, 4 or 5, wherein the support of the light-sensitive material to be processed is a reflective support. 7. The treatment agent contains 0.1 to 3.0 mol / l of a compound selected from the compounds represented by formulas (1) to (3) and a thiocyanate salt. Item 7. A method for processing a silver halide photographic light-sensitive material according to Item 1, 2, 3, 4, 5 or 6. 8. The treatment agent contains thiocyanate, as claimed in any one of claims 1, 2, 3, 4, 5, 6 or 7.
The method for processing a silver halide photographic light-sensitive material described in 1 above. 9. A bleach-fixing agent for silver halide photographic light-sensitive materials, which is substantially free of thiosulfate. 10. The silver halide photographic light-sensitive material according to claim 9, which contains at least one ferric complex salt of the compounds represented by the general formulas (K-1) to (K-3). Bleach-fixing agent for materials. 11. A bleach-fixing composition for silver halide photographic light-sensitive materials according to claim 10, which contains a ferric complex salt of a compound represented by the general formula (K-1), wherein l = 3. Agent. 12. The halogenated product according to claim 9, 10 or 11, containing at least one selected from the compounds represented by the general formulas (1) to (3) and thiocyanate. Bleach-fixing agent for silver photographic light-sensitive materials. 13. A compound selected from the compounds represented by the general formulas (1) to (3) and a thiocyanate is 0.1:
~ 3.0 mol / l is contained.
A bleach-fixing agent for silver halide photographic light-sensitive materials as described in 1. 14. A bleach-fixing agent for a silver halide photographic light-sensitive material according to claim 12, which contains a thiocyanate. 15. A method of processing a silver halide photographic light-sensitive material, comprising a step of processing with the bleach-fixing agent according to claim 9. 16. The processing time of the step is 1 second or more, 20
16. The method for processing a silver halide photographic light-sensitive material according to claim 15, which is less than a second.