JPS61112146A - Processing method of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To process quickly and easily a titled material, to recover easily silver at high efficiency and to make possible the processing with excellent image preservability by incorporating >=1 kinds among compds. of specific 5 groups together with the ferric complex salt of an org. acid into a bleach-fix bath. CONSTITUTION:>=1 Kinds among the compds. expressed by the formulas I, II, III, IV and V [Q is the atomic group necessary to form a heterocycle contg. >=1 N atoms (including the ring in which 5-6-membered unsatd. rings are condensed to at least one of these rings), R<1> is H, alkyl of 1-6 C, cycloalkyl, etc., A is the group expressed by the formula VI, etc., Y is >N- or >CH-, Z is H, alkali atom, NH2, etc., B is alkylene of 1-6 C, R<2>, R<3>, R<4>, R<5>, R<6> and R<1> are respectively H, alkyl of 1-6 C, OH, COOH, NH2, etc.] are incorporated together with the ferric complex salt of the org. acid into the bleach-fix bath of a silver halide color photosensitive material. The desilvering rate of the high-sensitivity photosensitive material is thus improved, the efficiency of the silver recovery is improved and the bleach-fix bath is stabilized.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a color photographic processing method, and in particular to a desilvering process for silver halide color photographic light-sensitive materials (hereinafter simply referred to as light-sensitive materials) with a simplified reduction bath. Regarding.

[Conventional technology]

After exposure, the photosensitive material is subjected to color development, bleaching, fixing, washing and/or stabilization. In the bleaching process, bleaching and fixing have conventionally been carried out in the same bath for the purpose of speeding up and simplifying the process in the case of light-sensitive materials that have a low silver content and do not contain silver iodide. Such processing is known as bleach-fixing.

By the way, we have started construction on bleached windows! In the case of /c, various problems arose due to the coexistence of bleaching agents, which are oxidizing agents, and preservatives, such as fixing agents and sulfites, which are reducing agents.

Because of this, it is not possible to perform stable ratio processing and special high-sensitivity photography.
Please note that processing of 5 materials is known to be difficult.

For example, if a relatively strong bleaching agent is added to increase the redox potential of the solution in order to increase the bleaching speed, the fixing component will be easily oxidized and sulfurized, and in severe cases, silver sulfide will be generated.
This can lead to irreparable accidents.Also, if the concentration of the fixing agent is increased too much in an attempt to increase the fixing speed, the fixing speed will actually decrease and become the rate-limiting step of the bleach-fixing reaction, which will slow down the processing speed. It may fall.

This is why red blood salts, persulfate salts, bromate salts, etc., which have high oxidizing power cannot be used, and organic acid ferric complex salts, etc., which have weak oxidizing power, have to be used.

That is, it can be seen that the bleach-fix solution has the disadvantages of low stability and insufficient bleaching performance in terms of rapidity, and therefore has not been put to practical use as a treatment for high-sensitivity photosensitive materials.

In general, the lower the pH, the higher the desilvering rate of the bleach-fix solution;
It is known that it decreases with an increase in

Normally, a bleach-fixing process is performed directly after the color developing process, so a high-pH color developing solution is brought in, which tends to increase the pH of the bleach-fix solution and cause fluctuations in bleach-fixing reactivity. Moreover, since the pH in the film is high, there is a drawback that the bleach-fixing speed at the initial stage of burnout is slow. In recent years, a replenishment method for bleach-fixing processing has been introduced, which is a so-called non-regenerating method that only replenishes the fixing agent necessary to complex the components lacking in the bleach-fixing solution and the silver ions that are eluted when processing photosensitive materials. When this method was adopted, it was found that the replenishment time for bleach-fixing is extremely small, and that when the silver ion concentration in the bleach-fix solution increases during continuous processing, the fixing speed can be significantly suppressed.

Therefore, it is desired to develop a rapid processing method that increases the fixing speed of a bleach-fixing solution by using the above-mentioned ethylenediaminetetraacetic acid i12 iron complex salt and has an excellent bleach-fixing speed.

In order to solve these shortcomings, make it easier to manage the bleach-fix solution, and solve the various problems mentioned above, we divided the bleach-fix solution into two tanks and used a countercurrent system to supply the fixing agent to the first tank. However, a method has been proposed in JP-A-58-105148 in which bleaching agent is mainly supplied to the latter tank while the overflow liquid is allowed to flow from the latter tank to the former tank and discharged from the former tank. However, in these methods, the first tank is essentially a bleach-fix tank, and the only way to supply fixing agent to the second tank is to bring in the photosensitive material, and the second tank essentially has the composition of a bleaching solution. Even if metallic silver is bleached in the later stage tank, problems such as poor fixing are likely to occur, and the silver thiosulfate complex brought in from the earlier stage tank may form insoluble salts and precipitate due to insufficient fixing agent, or the fixing agent may oxidize. Since it is easily decomposed by chemical agents, it has the disadvantage of forming silver sulfide, which can lead to serious failures.

On the other hand, the pre-stage tank has a high concentration of silver ions, a sufficient supply of fixing agent and preservative, and it can be said that the preservability of the liquid and the silver recovery efficiency are certainly high. However, although the silver recovery efficiency is as high as that of a low-concentration silver-containing solution, it is essentially a bleach-fix solution containing a bleaching agent, and the silver recovery efficiency cannot be dramatically improved.

This is because, in the iron wool substitution method, the iron wool is oxidized and dissolved by the ferric salt, and the portion that is not used for silver substitution becomes extremely large. In the electrolytic recovery method, the reduction of ferric salt at the cathode has priority over the reduction of silver, resulting in a decrease in current efficiency, and furthermore, the electrodeposited metallic silver is
This is because the ferric salt causes re-dissolution, and the presence of the ferric salt is an important problem in both cases. However, Japanese Patent Application Publication No. 1983-
The method of No. 105148 only divides the bleach-fix solution into two parts and increases the silver ion fjk degree in the former tank, but does not solve the fundamental problem. In particular, in the bleach-fix solution for printing photosensitive materials, which has a low silver content, the silver ion concentration accumulated is 10
．． Although it is less than 9/l and does not pose a major problem, in bleach-fix solutions for photosensitive materials for high-sensitivity photography, the accumulated silver ion strength is expected to be as high as 10 to 3 ol/l, and the desilvering reaction will be significantly reduced. It also has some drawbacks.

In order to solve these drawbacks, or to enhance the stopping effect after color development and prevent bleaching stains, etc.
In addition, in order to eliminate the need for recovering silver in a bleach-fix solution and to facilitate recycling, acidic fixing treatment has been carried out as a pretreatment for a bleach-fix solution for a long time. In this case, it has been said that it is particularly preferable to perform acidic fixing treatment. These methods are described in Japanese Unexamined Patent Publication No. 48-49'437.

However, in this method, the pre-fixing solution and the bleach-fixing solution have completely different compositions and have different pH values, so each replenisher is required from a separate kit. The adjustment, dissolution, and management of replenisher and replenisher become extremely complicated, and go against the trend of the era of temperature reduction. By allowing the overflow solution from the pre-fixing tank to flow into the bleach-fixing tank, the pre-fixing solution and bleach-fixing solution replenishers are filled with fixing agent and bleach, which are packaged separately as a bleach-fixing kit. It was proposed in Japanese Patent Application No. 172,995/1986 that each of these can be used as is, simplifying replenishment, and solving the above problems.

However, since the pre-fixing process requires a processing time of at least 10 seconds or more and 3 minutes or less, there is a drawback that speed is impaired.

On the other hand, it has been proposed to add various bleaching accelerators to bleaching solutions or bleach-fixing solutions that use metal complex salts of organic acids such as ethylenediaminetetraacetic iron (III) complexes as a bleaching agent. ing. Examples of such bleaching accelerators include thiourea derivatives as described in Japanese Patent Publication No. 45-8056, aliphatic amines as described in Japanese Patent Publication No. 46-556, and as described in Japanese Patent Publication No. 46-280. British Patent No. 1,138
．． Examples include five-membered ring meridyl compounds as described in Swiss Patent No. 842, thiourea derivatives, thiazole derivatives, thiadiazole derivatives as described in Swiss Patent No. 336.257.

However, many of these bleach accelerators do not always have a satisfactory bleach accelerating effect when used with conventional processing methods, and even if they have an excellent bleach accelerating effect, they lack stability in the processing solution. 7'Lt- has short useful life and cannot withstand long-term storage, or when it is included in the so-called pre-bath used in the process before processing with bleach or bleach-fix solution, bleaching can be accelerated. Many of them have drawbacks such as not being effective.

In addition, German Patent No. 213,940 proposes that onium compounds can be used as bleach accelerators. However, although these onium compounds have a bleaching accelerating effect, the effect is still not sufficient, especially when a metal complex salt of an organic acid is used as a bleaching agent. .

On the other hand, the present inventors previously discovered diethylenetriaminepentaacetic acid iron(III) as a bleaching agent that has relatively high oxidizing power among aminopolycarboxylic acid iron(m) complex salts in addition to ethylenediaminetetraacetic acid iron(m) complex salts. I discovered a complex salt. This iron (
m) Complex salts are characterized by rapid silver bleaching and reaction when the pH is high, especially above 9H4. However, even with this diethylenetriaminepentaacetic acid iron (m) complex salt, the bleaching speed is insufficient as a bleaching agent for ultra-high sensitivity silver halide color photographic light-sensitive materials, and the required speed cannot be sufficiently achieved. It became clear that the friend could not.

Nineth, the present inventor applied the general formula (1) of the present invention to a treatment solution having bleaching ability containing diethylenetriaminepentaacetic acid ferric complex salt.
It was discovered that the bleaching of current silver was significantly accelerated by adding the compound (5) above, and he first proposed this technology. When silveride emulsions were used, it was found that the bleaching techniques described above resulted in an insufficient bleaching speed. Especially ultra-high sensitivity, As human sensitivity 400 or more, especially 1000
Friend who knows that more than enough is not enough.

[Purpose of the invention]

The present invention has been made in view of the above-mentioned circumstances, and its purpose is to improve the bleaching properties of high-sensitivity photosensitive materials in a temperature-reduced processing step and to provide a processing step that speeds up the desilvering process. It is to be. Other purposes will become clear from the description below.

[Structure of the invention]

The object of the present invention is to provide a method in which a light-sensitive material is color-developed after exposure, subsequently treated with a pretreatment solution, and then treated with a bleach-fix solution, in which the bleach-fix solution contains at least one organic acid @ di-iron complex salt. and the pretreatment solution and/or the bleach-fix solution has the following general formula (υ, (2゜(3), (41 or (5)
This is achieved by a method for processing a silver halide color photographic material, which is characterized by containing at least one compound represented by the following.

General formula (1) General formula (2) General formula (3
) General formula (4) General formula (5) %Formula% In the above general formula, Q is a hetero Jjl containing one or more N atoms
(including those to which at least one 5- to 6-membered unsaturated ring is fused) represents the atomic group necessary to form
The hetero fIIFi substituent may be present, and ntrivalent substituted or unsubstituted hetero product residues (5 to
M represents a divalent metal atom, and B represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms. where X and X' are each =3. =Q or =NR
"represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
Cycloalkyl group, aryl group, heterozygous residue (5-6
At least one member unsaturated ring is bonded thereto, and ) ma 几 represents an amino group, and Y is 〉N- or )CH
-, 2 represents a hydrogen atom, an alkali metal atom, an ammonium group, a substituted or unsubstituted amino group, a nitrogen-containing heteroterminal residue or -8-B-Y(, and s Represents a substituted alkyl group, R't! Hydrogen atom, substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, cycloalkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic residue Ht represents a group (including those to which at least one 5- to 6-membered unsaturated ring is fused) or a substituted or unsubstituted amino group;

Rm, R', R', R'U R'ld each has 1 M hydrogen atoms, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, and an anlu group having 1 to 3 carbon atoms. group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted alkenyl group.
,, (however, R,!: R', R"toR"x andhiR'
and R' may be cyclized with each other to form a substituted or unsubstituted heterocyclic residue (including one in which at least one unsaturated ring of 5 to 6 Jj is fused) H@ >YobiR? each represents ff1H to m4 and n (where % R''ld represents a substituted or unsubstituted alkyl group).

each represents an integer from 1 to 6, and m represents an integer from O to 6.

or represents an alkyl group (preferably carbon 1 to 4),
However, % Q' has the same meaning as Q' above. The compounds represented by the general formulas (1) to (5) include enolized compounds and salts thereof.

The bleach accelerator of the present invention is represented by the above general formulas (1) to 5), and typical examples thereof include, but are not limited to, the following.

[Listed compounds]

(1-!'1) (1-6) (1-
23') (1-24) (1-25
) (1-2fi)H) (] -]33 (1-34)(
1-3F+ ) (1-36)(]
-:47'j (1-38)(
2-S) (2-6) (2-N>
(2-12) (2i:()
(2-14) (2-26"I (2-26') j+11 (2-27"I H,N -C:5NHNHC8-NH.

(2-27') (2-:(2) H,N　　-08NH(CH,),NHC8-NH.

(2-3:4) 11. N-esNH(CH,), NHC+3-NH
.

H, N -CINH (CH, entered NHC8-NH.

(2-:(5) (2-; U7) (2-39> (2-48'j (2-49') (2-FtQ) (2-5!'i) (2-!’)7’) (2-60> ('2-62) 8 H, H.

(2-6Fi ') Goguchi (2・-79) Go υ υ Suυ Su (2-111'I (2-112) (
2-12 () (2-
124)su(, 2-125) (2-12fi)
Seki (2-1:43) (2-134) (2
--1 piece (7) (2-
138) N1-1 H,N -CH,CH,-88 (:4-3) HOOC,CHIC)I, , 5H OH,+OH,-SH Ru(:(-25) (3-261(3)
-:43) (4-1) cH.

CH.

Cl-1゜ CH.

■ CHl (5--1) (S-2)
Strike (5-5) (5-6) (Ft
-11) (5-12')(
fi -131 (5-14) υH (Fl -21) (5-22)
(,!'1 - 27) (5
-28) (:H,CH,C:UOH! NaO,S (!'i -39) (5-4F+ ”) (Fl
-46') CH.

(5-53) (s -54) (!I
-59) (5-60)(
5-63) (5-1i4)
(5-65) (5-f6)
-Figure - (5-67) (5-ti8
)(5-75) (Fi-7
6) Hl( (fi -791(5-1'lO) (5-s3) (s -s4
) (5-85) (S -86'j
(5-89) (S -90) (5-
91'J (5-92) (5-95
) (5-96”) (S-97
) (5-9'8) (Fl-99
) (Fi -100) (5-
101) (S -102) (Fl
-, 105) (5-106) NH, NH.

' (Ft -111) (S-113) (Fl -1211' (Fl -125) (5-12
6) HH (5-1:J, 9) (5-1
40) (5-145”j (5-1
46) (5-147) ' (5-1
48) (5-151') (5-1
52) (5-153) ('5 -1
54 ) (5-155) (5-
156') Goh (5-IFI5) (5-16
6) (5-167) (5-168
')it (F) -173) (5-174) -('5
J 175 ) Among the compounds represented by the above general formulas (1) to (5), the above (2-27), (2-142), (2
-143), (3-2), (3-3), (3-5), (
3-6), (3-33), (3-34), (5-71)
and (5-74) are particularly preferred.

All of the above compounds are known and can be easily synthesized by known synthetic methods.

The inventors of the present invention have repeatedly investigated a method for processing photosensitive materials containing silver iodide using a single-bath bleach-fix solution, which is a simple processing step, and which does not cause the various troubles mentioned above. In particular, when using a bleaching agent consisting of a ferric complex salt of an organic acid such as a ferric complex salt of an aminopolycarboxylic acid and a ferric complex salt of an aminopolymethylene phosphate at a high concentration, as the concentration increases, It was found that the fixing reaction was significantly suppressed. It was also found that the delay in the fixing reaction was caused by the delay in the diffusion of the fixing agent.
It was found that the delay in reaction formation forms the rate-determining step of the bleach-fixing reaction, and in particular, it significantly suppresses the initial reaction and forms an induction period. It has been found that this phenomenon is particularly noticeable in the processing of photosensitive materials containing silver iodide. Furthermore, it was found that, as a matter of course, it was suppressed as the amount of silver increased.

Moreover, this phenomenon is particularly observed in organic acid ferric complex salts such as aminopolycarboxylic acid ferric complex salts. /1 or more, especially 8o11
It was also found that it was significant at /1 or higher.

Based on this phenomenon, the present inventors previously proposed treatment with a processing solution having fixing ability as a pretreatment for bleach-fixing as an effective means of preventing suppression of the fixing reaction. Separate treatment baths do not meet the demands of the era of temperature reduction and simplification, resulting in complicated treatment.

Therefore, it has been proposed to solve the above-mentioned drawbacks by connecting the pre-fixing solution and the bleach-fixing solution in a forward flow manner and processing the overflow of the pre-fixing solution while flowing into the bleach-fixing solution. However, these methods have the drawback that the processing time is extended due to the pre-fixing reaction, and the speed is impaired.

In the present invention, after the treatment with the pretreatment liquid, a bleach-fixing treatment is performed, and the pretreatment liquid and/or the bleach-fixing liquid contains at least a compound represented by the general formulas (1) to (5) of the present invention. By containing one of them, rapid bleach-fixing properties and stable bleach-fixing processing were obtained. It has been known for a long time that the compounds represented by the general formulas (1) to (5) of the present invention have a bleaching accelerating effect, but when pre-treatment, especially pre-fixing treatment, silver halide is removed. Perhaps for this reason, the present inventor discovered that the bleaching promoting effect of this compound is extremely high. In particular, when the molecular weight of the organic acid of the ferric complex salt contained in the bleach-fix solution is 300 or more, a remarkable accelerating effect can be obtained.

Also, a significant accelerating effect can be obtained even in pre-fixing treatment in which silver ions are bleached at a low concentration.

Compounds represented by the above general formulas (1) to (5) (hereinafter,
The bleaching accelerator of the present invention only needs to be present when bleaching the silver image obtained by development, and for that purpose, it is preferable to add it to the bleach-fixing bath, or it may be added to the bleach-fixing bath prior to In other words, it is also preferable to incorporate the compound into the bleach-fixing bath by adding it to a pretreatment bath and bringing it into the photosensitive material. Alternatively, a method may also be used in which the compound is incorporated into the photosensitive material in advance during production and then eluted into the bleach-fixing bath.

The bleaching accelerator of the present invention may be used alone, or
Two or more types may be used in combination. Good results are generally obtained when the accelerator is added to the bleach-fix solution or pre-treatment solution in an amount in the range of about 0.01 to 100 II per II of the processing solution. However, in general, when the amount added is small, the effect of promoting bleaching is small, and when the amount added is larger than necessary, precipitation may occur and contaminate the photographic material being processed. 1 to 501, more preferably 0.05 to 201 per 1j of treatment liquid
．． Most preferably it is 0.1 to 10j per treatment liquid II.

When adding the bleaching accelerator of the present invention to the processing solution, it may be added and dissolved as is, but it is common to dissolve it in water, alkali, organic acid, etc. before adding it, and add it as necessary. Even if it is dissolved in an organic solvent and added, the bleach-fixing effect is not affected at all.

Metal ions may be supplied to the bleach-fix solution of the present invention by any method. For example, it can be supplied in any form such as a halide, hydroxide, sulfate, carbonate, phosphate, acetate, etc., but it is preferable to supply it as a complex salt of the chelating agent using the compound shown below.

(A-1) Nickel chloride (A-2) Nickel nitrate (A-3) Nickel sulfate (A-4) Nickel acetate (A-5) Nickel bromide (Mu-6) Nickel iodide (A-7) Phosphorus Nickel (A-8) Bismuth chloride (A-9) Bismuth nitrate (A-10) Bismuth sulfate (A-11) Bismuth acetate (A-12) Zinc chloride (A-13) Zinc bromide (A-14) Zinc sulfate (A-15) Zinc nitrate (A-16) Cobalt chloride (A-17) Cobalt nitrate (A-18)'Cobalt sulfate (A-19) Cobalt acetate (A-20) Cerium sulfate Ch-21) Chloride Magnesium (A-22) Magnesium sulfate (A-23) Magnesium acetate (A-24) Calcium chloride (A-25) Calcium nitrate (A-26) Barium chloride (A-27) Barium acetate (A-28) Barium nitrate (Person-29) Strontium chloride (A-30) Strontium acetate (A-31) Strontium nitrate (A-32) Manganese chloride (A-33) Manganese sulfate (A; 34)
Manganese acetate (A-35) Lead acetate (A-36) Lead nitrate (A-37) Titanium chloride (A-38) Stannous chloride (A-39) Zirconium sulfate (A-40) Zirconium nitrate (A-41 ) Ammonium vanadate (A-42)
Ammonium metavanadate (A-43) Sodium tungstate (A-44) Ammonium tungstate (A-45) Ammonium chloride (A-46) Aluminum sulfate (A-47) Aluminum acetate (A-48) Yttrium sulfate (A- 49) Yttrium nitrate (A-50) Yttrium chloride (A-51) Samarium chloride (A-52) Samarium bromide (A-53) Samarium sulfate (A-54) Samarium acetate (A-55) Ruthenium sulfate (A- 56) Ruthenium Chloride These metal compounds may be used alone or in combination of two or more. The amount used is preferably 0.0001 mol to 2 mol, particularly preferably 0.001 mol to 1 mol, per working liquid IAI as metal ions.

The bleaching accelerator of the present invention is represented by the general formula (1) to 5), among which R1, R3, R1,14XB1
, R', R'', ASB, ZXZ', RSR', and 8 and B', Island and Rs, & and - and QS Q
Heterocyclic residue formed by ', amino group, aryl group,
The alkenyl group and the alkylene group may each be substituted. Its substituents include alkyl groups, aryl groups,
Alkenyl group, cyclic alkyl group, aralkyl group, cyclic alkenyl group, halogen atom, nitro group, cyano group, alkoxy group, aryloxy group, carboxy group, sil group, alkoxycarbonyl group, aryloxycarbonyl group,
Sulfo group, sulfamoyl group, carbamoyl group, acylamino group, heterocyclic residue, arylsulfonyl group, alkylsulfonyl group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group, N-arylanilino group, Examples include N-acylanilino group, hydroxyl group, and mercapto group. Also, the above formula -t Rs + Re * A + Br
The alkyl group represented by Z + Z', R# R' may also have a substituent, and examples of the substituent include all of the nine listed above except for the alkyl group.

The bleach-fix solution of the present invention preferably contains a complex salt of an organic acid and ferric ion having a molecular weight (weight average molecular weight) of 300 or more (hereinafter referred to as an organic acid ferric complex salt).

The following are representative examples of the organic acids that form the organic acid ferric complex salt of the present invention.

(1) Diethylenetriaminepentaacetic acid (Il&=393.
27) (2) Diethylenetriaminepentamethylenephosphone (Mv=573.12) (3) Cyclohexanediaminetetraacetic acid (Mwr=364
．． 35) (4) Cyclohexanediamine tetramethylene phosphonic acid (Mw=508.23) (5) Triethylenetetramine major acetic acid (Mw=494.
45) In the method of the present invention, the treatment with a pretreatment liquid refers to the treatment with a treatment liquid that does not have at least a bleach-fixing function, which is between the treatment with a color developing liquid and the treatment with a bleach-fixing liquid. . The processing may include, for example, processing such as stopping the photosensitive material, washing with water, fixing, and impregnating or adhering the bleaching accelerator of the present invention to the light-sensitive material.

In the present invention, the bleach accelerator of the present invention is used in the pretreatment liquid and/or
Or it is contained in the bleach-fix solution, but the pre-treatment solution is
In the above cases, at least one of the baths (of the same type or different types of solutions) and/or the bleach-fixing solution may contain the bleach accelerator of the present invention.

Pretreatment liquids of various compositions can be used in the present invention. The pretreatment liquid with the simplest composition is
Although it is an aqueous solution in which the bleach accelerator of the present invention is simply dissolved, acids such as acetic acid and boric acid, alkalis such as sodium hydroxide,
Alternatively, an aqueous solution appropriately containing salts such as sodium sulfite, sodium acetate, sodium thiosulfate, sodium borate, sodium carbonate, and sodium bicarbonate can also be advantageously used as the pretreatment liquid. Any 9H can be used as the pretreatment liquid, and any of them can effectively produce the effects of the present invention, but if the pH is too high, stain may occur, so 9H with a pH of 12 is generally used. Preferably used below.

In the pretreatment liquid, if necessary, a suspending agent made of various chelate compounds, a hardening agent made of various compounds including alum and aldehyde, pI (buffer,
It may contain fixing agents such as halogen salts, antioxidants such as sulfites, hydroxylamine, hydrazine, etc., swelling inhibitors such as sodium sulfate and magnesium sulfate, surfactants, and the like. The pretreatment liquid can be obtained by, for example, washing with water, stopping treatment, stop-fixing treatment, etc., and the effects of the present invention can also be obtained by adding the bleach accelerator of the present invention to such a pretreatment liquid. However, when the bleach accelerator of the present invention is contained only in the pretreatment solution, it is preferable that the pretreatment solution be used immediately before the bleach-fix solution.

In the method of the present invention, the pretreatment liquid used in the prebath of the bleach-fix solution does not substantially contain a bleaching agent (specifically, it does not contain a bleaching agent (specifically, 0.01%).
2 mol or less, more preferably 0.05 mol or less, most preferably 0.001 mol or less), and preferably has the 511 ability of silver halide. In this case, since most of the silver salt is dissolved here, the silver concentration is significantly higher than in the latter stage tank, so of course the silver recovery efficiency is high and desirable, but since it does not contain bleach, metal replacement method, electrolysis method, The efficiency of any silver recovery method such as ion exchange method or electrodialysis method is extremely high.

In addition, the effect of pH fluctuation due to the introduction of the color developer is virtually nil since the pre-bath mainly consists of the fixer composition, and it is rather preferable that it be mixed in at 5% or more, especially 10% or more.

Furthermore, the pH in the film after color development is high and inhibits the bleach-fixing solution reaction, but since there is pre-fixing, there is an advantage that there is little influence on the silver reaction in the film.

In the present invention, the pretreatment solution and the bleach-fix solution (PI) may be different or may be the same, and the pretreatment tank solution and replenisher should be used in order to neutralize color development. low pH
The pH of the bleach-fix solution in the bleach-fix tank is preferably higher than that in the pretreatment. In any case, pi can be arbitrarily selected as needed, and the optimum value can be selected to achieve the above-mentioned purpose. Preferably 3 to 8.5, particularly preferably 6 to 8.5
The pH of the pretreatment liquid is preferably Vi2 to 13, more preferably f'i, when the liquid to be drained is a liquid without fixing ability.
It is in the range of 3 to 10, particularly preferably 4 to 9, and when the drained liquid has fixing ability, it is preferably in the range of 2 to 9.01, and more preferably in the range of f13 to 8.

When the pretreatment liquid has the ability to fix silver halide, it is preferable that the treatment is performed while recovering silver, and an electrolysis method, an ion exchange method, or an electrodialysis method is usually used.

In these silver recovery methods, it is preferable that silver be processed while being continuously recovered by an in-line system, and as a result, silver recovery in a bleach-fix solution in a subsequent tank is not necessary.

It is desirable that air oxidation of the bleach-fix solution in the subsequent tank be carried out efficiently, and forced aeration can be performed.

In the present invention, when the pre-processing liquid has silver halide fixing ability, the processing liquid (hereinafter, the processing liquid is referred to as the pre-fixing liquid, the bath containing the processing liquid is referred to as the pre-fixing bath, and the processing tank containing the processing liquid is referred to as the pre-fixing liquid). It is preferable that the fixing tank (also referred to as a fixing tank, etc.) is mainly supplemented with a fixing agent, and the bleach-fixing solution is mainly supplemented with a fixing agent and a bleaching agent.
Within a range not exceeding 50% of the total amount used, preferably 30%
Bleach can be supplied and replenished to the pretreatment tank within a range not exceeding %. The amount of bleach used in the bleach-fixing solution of the present invention is 601 or more, preferably 8oI per 11 of the processing solution.
! Above, it is particularly preferably used at 90.9 or above.

Preferred bleaching agents used in the present invention are ferric complex salts of organic acids, especially ferric complex salts of aminopolycarboxylic acids or aminopolymethylene phosphoric acids, especially ferric complex salts of aminopolycarboxylic acids.

As a bleaching agent used in the bleach-fix solution of the present invention, preferred organic acids that form a ferric complex salt include the following.

These organic acids (eg, organic acetic acids, organic phosphonic acids, etc.) may be alkali metal salts, ammonium salts, or water-soluble amine salts. Specific representative examples of these include the following.

(1) Ethylenediaminetetraacetic acid (2) Ethylenediaminetetramethylenephosphonic acid (3) Diethylenetriaminepentaacetic acid (4) Diethylenetriaminepentamethylenephosphonic acid (5)
Ethylenediamine-N-(β-oxyethyl)-NXN
', N/-triacetic acid (6) Ethylenediamine-N-(β-oxyethyl)-NXN', N/-trimethylenephosphonic acid (7) Propylenediaminetetraacetic acid (8) Propylenediaminetetramethylenephosphonic acid (
9) Nitrilotriacetic acid (ltl) Nitrilotrimethylenephosphonic acid (11
) Cyclohexanediaminetetraacetic acid (12) Cyclohexanediaminetetramethylenephosphonic acid (13) Iminodiacetic acid (14) Iminodimethylenephosphonic acid (15)
Dihydroxyethylglycine citric acid (16) Dihydroxyethylglycine methylenephosphonic acid (17) Dihydroxyethylglycine tartaric acid (18) Ethyl ether diamine tetraacetic acid (19) Ethyl ether diamine tetramethylene phosphonic acid (20)! Recall ether diamine tetraacetic acid (
21 N Glycol Ether Diamine Tetramethylene Phosphonic Acid (22) Ethylene Diamine Tetrapionic Acid (23)
Ethylenediaminetetraacetic acid (24) Ethylenediaminetetramethylenephosphonic acid (25) Ethylenediaminetetraacetic acid disodium salt.

(26) Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt (27) Ethylenediaminetetraacetic acid tetrasodium salt (28) Diethylenetriaminepentaacetic acid pentasodium salt (29) Ethylenediamine-N-(β-okinethi#)-N, N', N '-Triacetic acid sodium salt (30)
Propylene diamine tetraacetic acid sodium salt (31
)2) Lilotriacetic acid sodium salt (32) Cyclohexanediaminetetraacetic acid sodium salt (33) Diaminoglobanol tetraacetic acid (34) Cyaminoglopanol tetramethylenephosphonic acid (35) Ethylenediamine-diortho-hydroxyphenylacetic acid (36) Ethylenediamine -Diortho-hydroxyphenylmethylenephosphonic acid (37) Ethylenediaminetetrakis (methylenephosphonic acid) (38) ) Liethylenetetraminehexaacetic acid (39) Triethylenetetraminehexamethylenephosphonic acid Preferred organic acids have a molecular weight of 300 or more. Bleaching agents are composed of these organic acids and ferric complex salts, and these complex salts may be ammonium salts, sodium salts, or potassium salts. It is also preferable to use one or more of these bleaching agents in combination.

In addition to these bleaching agents, the bleach-fix solution may contain a fixing agent and any of the following additives.

As fixing agents, compounds which react with silver halides to form water-soluble complex salts, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate;
Examples include thiocyanate salts such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thiourea, and thioether.

In addition to these fixing agents, fixing solutions and bleach-fixing solutions include ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, etc. sulfites, boric acid, borax, hydroxide)
It can contain one or more pH buffers consisting of various salts such as IJum, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide.

Furthermore, alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride,
It is desirable to contain a large amount of a rehalogenating agent such as ammonium bromide. In addition, pH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be added to normal bleach-fix solutions may be added as appropriate. can.

When replenishing the bleach-fixing solution with the bleach-fixing film solution, in the present invention, it may be divided into at least two component solutions and then replenished. The amount of bleach used in one of the bleach-fixing replenishers (B) is 1! 0.2 mol or more is preferable, particularly preferably,
The amount is 0.4 mol or more and 1.5 mol or less.

Generally, aminopolycarboxylic acid ferric complex salts have low solubility, so it is not easy to prepare the above-mentioned concentrated solution by itself. potassium,
Add sodium borate, potassium metaborate, and sodium metaborate to pH.

A concentrated solution can be obtained relatively easily by increasing the .

As the thiosulfate preferably used in the other half of the bleach-fix replenisher, potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, etc. are useful, and the amount used is 7 equivalents of the bleach-fix replenisher AI! The amount is preferably 71.0 mol or more, particularly preferably 1.5 mol or more and 5.0 mol or less.

In addition, sulfites include ammonium sulfite, potassium sulfite,
Ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, etc. are useful, and the amount used is 0.3 per Al of bleach-fixing replenisher. The amount is preferably 0.4 mol or more and 3.5 mol or more.

The above concentration range is a preferable range from the viewpoint of variation in the liquid composition of the bleach-fixing bath and bleach-fixing ability.

The pH of the bleach-fixing replenisher is preferably maintained at 4.0 to 9.0.

More specifically, since a highly alkaline color developing solution is carried into the bleach-fixing bath by the sensitive material being processed, in order to maintain the pH of the bleach-fixing solution mentioned above, the pH of bleach-fixing replenisher A is (The pH of the bleach-fixing bath is adjusted by adjusting the pH of
This is because it is preferable to maintain constant. of the bleach-fix replenisher containing ferric amino acid complex salt) is substantially p.
Setting H to 6.5 or less is disadvantageous from the point of view of solubility, so keep it higher than that, and therefore the bleach-fixing replenisher (4) containing thiosulfate and sulfite is suitable for both solubility and stability. Since the pH can be lowered to around 4.0, it becomes possible to maintain the pH of the bleach-fix bath at a desired value by adjusting the pH value of the bleach-fix replenisher (B). Of course, the pH value of these replenishers must be changed depending on the amount of replenishment.

It is preferable not to add bleach to the bleach-fixing replenisher) in view of the storage stability of the processing solution.

The bleach-fix replenisher (B) preferably contains a ferric complex salt of an organic acid such as the aminopolycarboxylic acid as described above and a suitable alkaline agent, as well as a pH buffer such as ammonium borate or ammonium nitrate; Non-chelating agents for aminopolycarboxylic acids other than the above-mentioned ferric complex salts, such as ethylenediaminetetraacetic acid diammonium salt, can be included. In addition, the bleach-fixing replenisher (B) contains fixing agents such as thiosulfates, sulfites, glacial acetic acid, non-chelating agents for sulfamino acids and aminopolycarboxylic acids, boric acid, phosphoric acid, sulfuric acid, etc. pH buffers, thiocyanates, amines, silver halide solvents such as mercaptotriazole, known stain inhibitors such as 1-phenyl-3-pyrazolidone, formamidinosulfinic acid, paraphenylenediamine,
Polyalkylamine compounds (, British Patent No. 1.192,
481) polyamine compound (fF Kosho 45
-8836), ethylene oxides (described in Akita Patent No. 966.410), nitrogen-containing heterocyclic compounds (described in Kyokoku Percentage No. 1.290.812)
Known additives such as can be included.

In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix tank and the bleach-fix replenisher storage tank as desired, or an appropriate oxidizing agent such as peroxide may be used. Hydrogen, bromate, persulfate, etc. may be added as appropriate.

When carrying out the method of the present invention, silver may be recovered from the pretreatment solution and/or the bleach-fix solution by a known method. For example, electrolysis method (described in French Patent No. 2.299.667)
, precipitation method (described in %KOKAI Publication No. 52-73037, Kyokoku Patent No. 2.331.220), ion exchange method (
Described in Japanese Patent Application Laid-Open No. 51-17114, Strong Country Patent 2.54
8゜237) and the metal substitution method (British Patent No. 1)
．． 353.805 specification) etc. can be effectively used.

In the processing method of the present invention, it is preferable that the processing tank containing the pre-treatment liquid and the processing tank containing the bleach-fixing liquid are connected in a downstream manner. It is preferable to have the ability.

After bleach-fixing, stabilization treatment may be performed without washing with water, or washing with water and subsequent stabilization treatment may be performed. In addition to the above-mentioned steps, known auxiliary steps may be added as necessary, such as dura mater, neutralization, black-and-white development, reversal, and washing with a small amount of water.

A typical example of a preferred treatment method includes the following steps.

(1) Color development → pre-treatment (fixing) → bleach-fixing → first stable → second stable → third stable (2) color development → pre-treatment (fixing) → bleach-fixing → washing with a small amount of water → washing with water (3) color development Development → Pre-treatment (fixing) → Bleach-fixing → Washing → Stable (4) Color development → Pre-treatment (fixing) → Bleach-fixing → Stable (5
) Color development → pre-treatment (fixing) → bleach-fixing → first stabilization → second stability (6) color development → pre-treatment washing → fixing → bleach-fixing → washing (
(or stable) (7) Color development → stop pre-treatment → fixing → bleach-fix → Anonymous However, in each process, pre-fixing and bleach-fixing steps in processing include forward flow connection.

In addition, in the above specific examples, when the stabilization process is divided into two or more, each may be performed using the same type of liquid or different types of liquids, and the stabilizing liquid may be a solution other than the normally used bleach-fixing liquid components. These include those with a function to prevent uneven water droplets, and those with a function to prevent uneven water droplets.

It is preferable to add various inorganic metal salts to the bleach-fix solution of the present invention; it is also preferable to add these inorganic metal salts after forming them into metal complex salts together with various chelating agents.

The effects of the present invention are most effective in processing light-sensitive materials having a silver halide emulsion layer containing at least 0.3 mole of silver iodide. Especially preferable t! :A photographic material having a silver halide emulsion layer containing 2.0 mol% or more of silver iodide.A more effective photographic material has an emulsion consisting of core-shell type grains and an emulsion consisting of tabular silver halide grains. can give.

As a core-shell silver halide particle, JP-A-57-1
The method of the present invention is effective for photosensitive materials having silver halide grains as described in No. 54232.
In particular, the silver halide composition is 0.3 to 20 mol% silver iodide.
More effectively, the method of the present invention is suitable for light-sensitive materials having core-shell based silver halide grains having cores consisting essentially of silver iodobromide in an amount of 0.5 to 20 mol %.

In addition, as tabular silver halide grains, JP-A-58-
No. 113930, No. 58-113934, No. 58-1
No. 27921, No. 58-108532, etc., including those manufactured by the method described in the same, particle size of 0.5 μm or more,
The method of the present invention is particularly suitable for processing photosensitive materials having a diameter of 0.6 to 6 .mu.m.

Furthermore, the method of the present invention can also be preferably applied to photosensitive materials containing epitaxially bonded silver halide grains as described in JP-A-53-103725 and the like.

The silver halide emulsion used in the light-sensitive material processed by the method of the present invention may contain various commonly used additives depending on the purpose. For example, stabilizers and antifoggants such as asaine thenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts, polyhydroxy compounds, etc.: aldehyde, aziridine, inoquinazole, vinylsulfone, acryloyl, alphoshiimite, Maleimide type, methanesulfonic acid ester type,
Hardening agents such as triazine type: In-situ accelerators such as benzyl alcohol and polyoxyethylene compounds; Image stabilizers such as Chroman type, Claman fruit, bisphenol, 1%, and phosphite type; Wax, glycerides of higher fatty acids ,
There are lubricants such as higher alcohol esters of higher fatty acids. In addition, anionic, cationic, nonionic, or A variety of both sexes can be used. Moreover, it is particularly preferable that these surfactants are eluted into a processing solution having bleaching ability. As antistatic agents, diacetyl cellulose, styrene perfluoroalkyl lithium maleate copolymer, styrene-
An alkali salt of a reaction product of maleic anhydride [copolymer and p-aminobenzenesulfonic acid] is effective. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. It is also possible to use colloidal silicon oxide.

Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc., and other monomers having ethylene groups.

Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers and alkyl vinyl ether-maleic acid copolymers.

Supports for photosensitive materials include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, polystyrene, etc. The material is appropriately selected depending on the intended use of each silver halide color photographic light-sensitive material.

The silver halide emulsion to which the present invention is applied is a red-, green-, and blue-sensitized emulsion containing a combination of cyan, magenta, and yellow couplers in order to be applied to a color photosensitive material. The methods and materials used for photosensitive materials such as

The photosensitive material to which the method of the present invention can be applied is an internal development method (U.S. Patent No. 2.376
．． No. 679, U.S. Pat.
, 590.970). Further, as the coloring agent, any coloring agent generally known in the art can be used.

For example, cyan coloring agents are those based on a naphthol or phenol structure and form indoaniline dyes through coupling, magenta coloring agents are those having a skeletal structure of a 5-pyrazolone ring with an active methylene group, and yellow coloring agents are As such, those having an acylacedoanilide structure such as benzoylacedoanilide and bivalylacetanilide having an active methylene chain, with or without a substituent at the coupling position can be used. Thus, as the coloring agent, both the so-called 2-way ffi type coupler and the 4-way type coupler can be used.

The aromatic primary amine color developing agent used in the color developing solution used before processing with the bleach-fix processing solution of the present invention is a known aromatic primary amine color developing agent that is widely used in various color photographic processes. things are included. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Further, these compounds generally have a content of about 0.0% for the color developer 11. II to about 301, more preferably about 11 to about 15.9 in 11.

Examples of aminophenol thread developers include 〇-aminophenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like.

A particularly useful aromatic primary amine color developer is N.

It is an N-dialkyl-p-phinidine diamine compound, and the alkyl group and phenyl group may be substituted or unsubstituted.

Among them, particularly useful compounds include N,N-diethyl-p-phenylenediamine salt rR salt, N-if loop
-phenylenediamine salt R salt, N,N-,) Methyl-p-phenylenediamine hydrochloride, 2-amino-5-(
N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-
Hydroxyethylaminoaniline, 4-amino-3-methyl-N, N-ethylaniline, 4-amino-N-(
Examples include 2=methoxyethyl)-N-ethyl-3-methylaniline-p-)luenesulfonate.

The color developer used before the processing of the present invention contains, in addition to the aromatic primary amine color developer, various components normally added to color developers, such as sodium hydroxide and sodium carbonate. , alkaline agents such as potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, diethylenetriami-75 vinegar #1-
A water softener and a thickening agent such as hydroxyethylene-1,1-diphosphonic acid may optionally be included. The pH of the color developer is usually 7 or higher, most commonly about 10 to about 13.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited thereto.

Example-1 Average grain size 1.0 consisting of silver iodobromide containing 3 mol% silver iodide
Using a silver iodobromide emulsion obtained by shelling silver bromide with a shell thickness of 0.05 μm onto μm emulsion grains, gold sensitization and sulfur sensitization were performed, and after aging, 4-hydroxy-6-methyl- After adding 1,3,3m,7-tetrazaindene, a sample was prepared as follows so that the amount of silver was 112In9/100d.

Anhydro-3,31-di(3), a red-sensitive sensitizing dye
-sulfopropyl) -5,57-dichloroo-9-ethylthiacarbocyanine hydroxide (dye p-1)
285m9/1 mol AgX, Anhuto 0-3.3
7-di(3sulfopropyl)-4,5,4', 5
'-dibenzothiacarbocyanine hydroxy)' (color IWp-2) 38.5 li/1% AgX and anhydro-1,3-diethyl-3'-(3-sulfopropyl)-5-trichloromethyl- , i/, s/-benzobenzimidazolothiacarboxyanine hydroxide (dye p-3) 116 to 71 moles Optical sensitization was performed using AgX. This photographic emulsion was coated with 2-(α, α, β, β, γ, γ, δ, δ -octafluorohexanamide)-5-(2-(2,4-di-amylphenoxy)hexanamide]7--norwotricresyl phos7ate A dispersion prepared by dissolving the coupler in a conventional manner and dispersing it in a protective manner was added thereto in an amount of 0.3 mol of coupler per 1 mol of AgX.Furthermore, as a stabilizer, 4-hydroxy-6-methyl-1,3゜3a,7 -tetrazaindene, poly-N-vinylpyrrolidone as a physical development inhibitor, and a fog inhibitor were added and coated onto a subbed cellulose acetate film.

The sample was exposed to light in a conventional manner and subjected to the following development treatment.

Color development was performed for 3 minutes and 15 seconds, pretreatment bath for 1 minute, bleach-fixing for 1 minute or additional, washing with water for 2 minutes, and stabilization treatment for 1 minute, followed by drying.

Each treatment was carried out at 37.8° C., and each treatment solution was treated with *a according to the following formulation.

[Color developer]

Potassium carbonate 30I! Sodium sulfite 2. ON Hydroxyamine sulfate 2.0.9 Potassium bromide 1.2 Sodium II hydroxide 3.41 N-Ethyl-N-β-hydroxyethyl-3-methyl-4-aminoaniline hydrochloride 4.61 Add water 1
! The pH was adjusted to 10.1 using IJum (hydroxide).

[Pre-treatment liquid (1)] Sodium sulfite 10.019
Bleaching accelerator shown in Table-1 1. The pH was adjusted to 11 with OII water to 6.8.

[Pre-treatment liquid (2)] Ammonium thiosulfate 100. OII
Sodium sulfite 10. The bleaching accelerator shown in OJ Table-1 was adjusted to 1.0% with F water, and pi was adjusted to 6.8.

[Bleach-fix solution (1)] Ethylenediaminetetraacetic acid iron ([) complex! 75.
011 Ammonium sulfite (50% dissolved K) 1o
, o, p ammonium thiosulfate (70% solution) 1
00.0.9 Table-1 shows bleaching accelerators
1.01! Water was added to make the solution 11, and the pH was adjusted to 7.2 with ammonium hydroxide.

[Bleach-fix solution (2)] A solution obtained by adding diethylenetriaminepentaacetic acid ferric complex salt instead of the ethylenediaminetetraacetic acid ferric complex salt of the bleach-fix solution (1).

[Stabilizing liquid]

Formalin (35% aqueous solution) 7.0I
L11-Hydroxyethyl 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 J
l,z-pentzinthiazolin-3-one 0. ll5
-Chloro-2-methyl-4-inthiazolin-3-one 0.11I Magnesium chloride 0.51! Add water to make it to 11.

Table 1 shows a comparison of the bleach-fixing completion times for each film to be processed using each bleach-fixing solution.

Table 1 As can be seen from Table 1, in the case where pretreatment is performed by the treatment method of the present invention (treatment step (1)), the treatment step (1) is to carry out bleach-fixing directly from color development treatment. It can be seen that the accelerating effect of the VS white accelerator is significantly more pronounced than the treatment with VS.

Furthermore, as shown in Table 1 above, the bleaching accelerator of the present invention was highly effective when added to the pretreatment liquid, and particularly showed a significant accelerating effect when the pretreatment liquid contained ammonium thiosulfate.

In addition, the bleaching agent in the bleach-fix solution is triethylenetetraminehexaacetic acid ferric complex salt, cyclohexa/diamine ferric acetic acid complex salt, and glycol ether diamine tetraacetic acid ferric complex salt, and nine is diethylenetriaminepentaacetic acid ferric complex salt. Almost the same results were obtained as in the case of .

Furthermore, bleach accelerators to be added to the pretreatment solution and/or butterfly bleach-fix solution can be added to exemplified compounds (1-1), (1-12), and (1).
-31), (2-1), (2-6), (2-26), (
2-30), (z-a3), (2-35), (2-53
), (2-79>, (2-1033, (3-1), (4
-1), (5-74), (5-108) and (5-13
8), but no difference was observed in the effect of the present invention.

Furthermore, although the pa of the pretreatment bath was changed to pH 4, PH 6, and pH 10, the effects of the present invention did not change.

Example 2 Using the same processing solution as in Example 1, continuous processing was performed with and without a pre-fixer.

However, the bleach-fix solution (2) is used, and the bleach accelerator is the exemplified compound (5-71), which is added to both the pre-fix solution and the bleach-fix solution, and the over 70% of the pre-fix solution is added to the bleach-fix solution. It was collected without being washed away.

The same light-sensitive material sample as in Example 1 was used, and the amount of bleach-fix solution replenished was 100 cII per sample. 10-Replenished. As a result, when there was no pre-fixing bath, precipitation occurred in the bleach-fix solution when the total replenishment amount was 1.8 times the bleach-fix tank capacity, but when there was pre-fixing, precipitation occurred. Shinakatsu friend. The bleach-fix solution from the pre-fixed reeds was stored for an even longer period of time, but no precipitation occurred and it was confirmed that it was stable for a long period of time. In addition, in the forward flow method in which the overflow solution of the pre-fixer is combined with the bleach-fix solution, the bleach-fix replenisher is divided into two parts, a fixer component and a bleach component, and the fixer component is replenished into the pre-fixer. Continuous long-term processing can be performed by replenishing only the bleaching component to the bleach-fixing solution, and replenishing the pre-fixing solution can be omitted.

Example 3 An example of the present invention will be described in detail with reference to drawings of a processing apparatus used in the method of the present invention and the comparative method. ' Fig. 2 shows the main parts of a color paper processing apparatus, and Fig. 1 shows the main parts of a color negative film processing apparatus. The conventional bleach-fixing method for color negative film has not been put into practical use, so it will be omitted here.

In FIG. 1, the color negative film processing apparatus 20 includes a color developing tank 4, a pre-fixing tank n1, a bleach-fixing tank, a washing tank wing, and a
The color developing tank 21 includes a replenisher supply pipe 21A and an over 70 pipe 2.
In addition to 1B, although not shown, it is equipped with a stirring means, a filter, a liquid temperature adjusting means, etc.

The pre-fixer tank 4 is in the bleach-fix solution and the overflow pipe 22C
They are connected in a forward flow manner so that the overflow liquid from the pre-fixing tank 4 flows into the bleach-fixing tank in the field.

Further, the fixing agent and the bleaching agent are supplied separately to the fixing replenishment tube 22A and the bleach-fixing replenishment tube 22B.
From the fixing replenishment pipe 22A, the bleach-fixing replenishment pipe 2 is connected to the processing tank n.
Replenisher liquid is supplied from 2B to each processing tank n. Bleach-fix tank overflow liquid Fi
The silver is discharged to the outside by 22D and the silver is recovered. Furthermore, although not shown, stirring means, liquid temperature adjustment means, etc. are provided. Further, hot water is supplied to the washing tank and stones from 24A, flows from 5 to 5 in a countercurrent method, and then flows through the drain pipe 24B. The stabilizing tank is supplied with replenisher through 26A, overflow is discharged through 26B, and further has stirring temperature adjustment means.

FIG. 3 is a diagram showing the processing form of color paper as found in JP-A-58-105148, which was devised to facilitate the management of bleach-fixing, and is shown as a comparative method. The apparatus shown in FIG.
It consists of

The basics are the same as in Fig. 1, and although the explanation will be omitted, the feature in Fig. 3 is that the bleach-fix replenisher containing both bleach and fixer is supplied to the second bleach-fix tank 13. The overflow liquid from tank 13 flows into the first bleach-fixing tank 12 through 12C in a countercurrent manner, and is finally discharged outside through 12D.

The bleach-fix replenisher is divided into two parts, a bleaching agent and a fixing agent, and the 16A white-fixing tank is mainly replenished with the fixing component, and the second bleach-fixing tank is mainly replenished with the bleaching component. Therefore, the replenishment method is exactly the same as in Fig. 1, and the difference in Fig. 2 is between the countercurrent method and the forward flow method.

That is, one of the fundamental differences between the comparative process and the process of the present invention can be found in the difference between the countercurrent system and the forward current system in the processing equipment.

This will be explained in detail by an experiment in which the same color film was processed using the respective apparatuses shown in FIG. 1 used in the method of the present invention and FIG. 2 used in the comparative method.

First, the color film used in the following experiment will be described.

Average grain size 1 consisting of silver iodobromide containing 3.6 mol% silver iodide
．． Average shell thickness of 0.05 μm for silver halide grains of 0 μm
Gold sensitization and sulfur sensitization were applied to a silver iodoemide emulsion having silver halide grains formed by shelling silver bromide of m, and 4-hydroxy-6-methyl-1,3,3m,7tetrazaindene was added. After that, a sample was prepared as follows so that the amount of silver was 112119/100d.

Anhydro-3,3'-di(3), a red-sensitive sensitizing dye
-sulfopropyl) -5,5'-dichloro-9-ethizothiacarbocyanine hydroxide (dye p-1)
285 da 1 mol AgX s anhydro-3,3'-
Di(3-sulfopropyl) -4,5,4', 5'
-dibenzothiacarbocyaenehydroxine (dye p
-2) 38.5ff + 9/ 1 mol Ag −
3) Optical sensitization was performed using 116 x 71 moles of AgX. In this photographic emulsion, 2-(α,
α, β, β=rmr+δ, --octafluorosanhexanamide)-5-(2-(2,4-di-amylphenoxy)hexanamide)phenol was dissolved in tricresyl phosphate and protected and dispersed by a conventional method. The dispersion was added in an amount of 0.3 mol of caplar per 1 mol of AgX.Furthermore, 4-hydroxy-6-methyl-1,3,3m, 7-titrazaindene was added as a stabilizer, and nophenyl-5- as a capri inhibitor. Mercaptotetrazole and poly-N-vinylpyrrolidone as a physical development inhibitor were added and coated on a subbed cellulose acetate film.

The color film sample thus produced was exposed to light in a conventional manner and subjected to the following development treatment.

[Development processing]

Color development 3 minutes and 15 seconds pre-fixing or 1st bleach-fixing 2 minutes 2nd bleach-fixing 6 minutes washing (1st) 1 minute (2nd) 1 minute stable 1 minute drying 3 minutes The processing solution has the following formulation. Using.

[Color developer]

Potassium carbonate 3019 Sodium sulfite 2.0 II Hydroxylamine sulfate 2.0 g 1- and Droyethylidene-1,1-diosphonic acid (60% aqueous solution) 1.0 N Magnesium chloride 0.3 g Hydroxyethyliminodiacetic acid 311 Bromide Potassium 1.2II Sodium hydroxide 3.4gN-ethyl-N-
β-Hydroxyfk-3-methyl-4-aminoaniline hydrochloride 4.6g Add water and IA! The pH was adjusted to 10.1 with sodium hydroxide.

[Color developer replenisher]

The potassium bromide in the color developer replenisher was adjusted to 0.91 J, and the pH was adjusted to 0.91 J.
was set to 10.20.

[Replenisher (4)] The pH was adjusted to 11 with water, and the pH was adjusted to 4.9 with ammonium hydroxide.

[Replenisher (A')]

Adjusted to.

[Replenisher (6)] Adjusted to.

[Pre-fixing tank liquid] (for the present invention) Replenisher (4) and water were mixed at a ratio of 1:1, and the pH was adjusted to 6.0 with potassium carbonate.

[First bleach-fixing tank solution] (for comparison) 1 part of replenisher (A), 1 part of replenisher (C) and 2 parts of water were mixed, and the pH was adjusted to 7. Adjusted to o.

[Bleach-fixing tank liquid] (for the present invention) Same as the first bleach-fix tank solution above.

[Second bleach-fixing tank solution] (for comparison) Same as the first bleach-fix tank solution above.

1 with water! Toshi 9.

The replenisher and Tajik solution had the same composition.

The amount of replenishment etc. is shown in Table 2. The amount of replenishment is 62-2 per millimeter of color negative film (width 35 Am).Next, the bleach-fixing method will be explained.

[In the case of the present invention]

Using the apparatus shown in FIG. 1, the pre-fixing tank solution is put into the front foot deposition tank 22, and the bleach-fixing tank solution is put into the bleach fixing tank MN'23. For the replenisher, add 2 parts of the replenisher (A') to the pre-fixer solution B.
2A according to the treatment. A replenisher solution ω) is supplied to the bleaching solution through 22B. The overflow liquid of pre-fixer n flows into the bleach-fix tank through 22C, and the overflow liquid of the bleach-fix tank is discharged through 22D.

[For comparison]

Using the apparatus shown in FIG. 2, the 1F111 white tank solution is put into the first bleach-fixing tank 12, and the second bleach-fixing tank solution is put into the 211th white-fixing tank. Replenishment is carried out in the same manner as in the explanation of FIG.
This differs from the case of the present invention using the apparatus shown in FIG. 1 in that it uses a countercurrent system in which the air is discharged through the air.

Processing was carried out using the two types of apparatuses described above under the conditions described above. The processing is continued until the volume of the replenisher supplied to the color developing tank reaches three times or more the capacity of the processing tank. The results were as follows.

(1) Desilvering time In the process according to the present invention, desilvering was completed in a total of 2 minutes during the bleach-fixing process for both the new solution and the running solution, but in the comparative process, desilvering was completed in 5 minutes (features) seconds with the new solution. Desilvering was no longer possible with Raninda liquid.

(2) Silver recovery effect The silver recovery efficiency of each of the present invention and comparative bleach-fix solutions was determined. Silver was recovered using electrolysis.

The device used was San Seiki BF-50.The efficiency was determined by current efficiency and is shown in Table 3.

Table 3 From the results in Table 3, when a pre-fixer is used as the pre-treatment liquid in the method of the present invention, the liquid in the pre-fixer tank is continuously guided to the electrolyzer and processed while recovering silver. This suggests that it is possible to efficiently recover most of the silver while preventing the silver from flowing into the bleach-fixing solution, and that a process that is much more favorable than conventional methods can be achieved. Any conventionally known method for recovering silver from the pre-fixer is extremely advantageous. Separately from this embodiment, the pre-fixing tank and bleach-fixing tank were separated by the method shown in Figure 1, and the overflow pipe 4 was
The bleach-fixing clearing time was further shortened by changing the method of discharging the overflow hole of C to the outside without guiding it to tank 23. However, the replenisher also refilled the bleach-fixing tester.

Furthermore, no coloring was observed in the image storage stability of the processed color film, and results were obtained in which both the dark fading resistance and the light browning resistance were similar.

〔Effect of the invention〕

(1) The desilvering processing speed of challenging light-sensitive materials is improved in a processing factory whose temperature is reduced.

(z When the pre-treatment liquid in the method of the present invention is a pre-fixing liquid, in addition to the above effects, stabilization of the bleach-fixing liquid,
This simplifies replenisher dissolution and replenisher kit configuration, and improves the efficiency of silver recovery.

[Brief explanation of drawings]

FIG. 1 is a schematic sectional view of a processing apparatus used in an example of the present invention, and FIG. 2 is a schematic sectional view of a processing apparatus used in a comparative example.

Claims (1)

[Scope of Claims] 1) A method in which a silver halide color photographic light-sensitive material is exposed, developed, and then treated with a pretreatment solution and then treated with a bleach-fix solution, wherein the bleach-fix solution contains at least one kind of contains an organic acid ferric complex salt, and the pretreatment solution and/or the bleach-fix solution contains a compound represented by the following general formula (1), (2), (3), (4) or (5). A method for processing a silver halide color photographic material, characterized in that it contains at least one type of silver halide. General formula (1) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (2) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (3) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (4) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (5) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the above general formula, Q is a heterocycle containing one or more N atoms (
R^1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, Represents a cycloalkyl group, aryl group, heterocyclic residue (including those to which at least one 5- to 6-membered unsaturated ring is fused), or an amino group, and A represents a ▲ mathematical formula, chemical formula, table, etc. There are ▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -SZ' or n_1-valent heterocyclic residue (5- to 6-membered unsaturated ring is at least X and X' each represent =S, =O or =NR'', R'' is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, Represents a cycloalkyl group, aryl group, heterocyclic residue (at least one 5- to 6-membered unsaturated ring may be fused thereto), or an amino group, R^2, R^3, R^4 , R^5, R and R^1 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, or an alkenyl group. represent, however,
R and R^1, R^2 and R^3, and R^4 and R^5 are each cyclized with each other to form a heterocyclic residue (at least one 5- to 6-membered unsaturated ring is fused to this). may also be formed. Y represents >N- or >CH-, Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, or ▲There are numerical formulas, chemical formulas, tables, etc.▼, and B represents carbon. Represents a number of 1 to 6 alkylene groups, M represents a divalent metal atom, Z' represents Z or an alkyl group, R^6 and R^7 each have a ▲ mathematical formula, chemical formula, table, etc. ▼ , ▲Mathematical formula, chemical formula,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, R^9 is an alkyl group or -(CH_2)n
_8SO^■_3 (However, R^9 is -(CH_2)nSO
When ^■_3, l represents 0 or 1), and G
^■ represents an anion). m_1 to m_4 and n_1 to n_8 each represent an integer of 1 to 6, and m_5 represents an integer of 0 to 6. R^8
represents a hydrogen atom, an alkali metal atom, ▲a mathematical formula, a chemical formula, a table, etc.▼ or an alkyl group, provided that Q' has the same meaning as Q above. Note that the compound represented by the above general formula includes enolized compounds and salts thereof. (2) The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the pretreatment liquid has a silver halide fixing ability. (3) The processing tank for the pre-treatment liquid and the processing tank for the bleach-fix solution are connected by a forward flow system, and the overflow liquid of the pre-treatment liquid is introduced into the bleach-fix solution for processing. A method for processing a silver halide color photographic light-sensitive material according to item 1 or 2. (4) A silver halide color photograph according to claim 1, 2 or 3, wherein the bleach-fix solution contains a complex salt of an organic acid with a molecular weight of 300 or more and ferric ions. How to process photosensitive materials. (5) 0.3 mol% of silver halide color photographic light-sensitive material
A method for processing a silver halide color photographic light-sensitive material according to claim 1, which comprises a silver halide emulsion layer containing the above silver iodide. (6) A method for processing a silver halide color photographic material according to claim 1, wherein the compounds represented by formulas (1) to (5) are the following compounds. ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, HS-CH_2-
CH_2-COOH, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas , chemical formulas, tables, etc.▼, or ▲mathematical formulas, chemical formulas, tables, etc.▼