JPH01221745A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the silver bleachability and processing stability of a sensitive material and the shelf stability of a dye image by adding a specified ferric complex salt to a bleaching soln. and a sulfite or sulfurous acid releasing compd. to a processing soln. having fixing ability. CONSTITUTION:A ferric complex salt of a compd. represented by formula I is added to a bleaching soln. and at least 0.1mol./l sulfite or sulfurous acid releasing compd. to a processing soln. having fixing ability. In formula I, each of A1-A4 is -CH2OH, -COOM or -PO3M1M2, each of M, M1 and M2 is H, Na, K or NH4, X is 2-5C optionally substd. alkylene and the total number of C atoms is >=3. When a sensitive material is processed with the solns., a dye image having superior shelf stability is rapidly obtd. and precipitation is suppressed.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and more specifically, the present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, it has excellent processing stability, improved storage stability of dye images, and rapid processing. The present invention relates to a method for processing a silver halide color photographic material (hereinafter sometimes simply referred to as a "photosensitive material") that is capable of processing.

[Background of the Invention] Processing of light-sensitive materials basically consists of two steps: color development and desilvering, and desilvering consists of a bleaching and fixing step or a bleach-fixing step. In addition to this, rinsing treatment, stabilization treatment, etc. are added as additional treatment steps.

The processing solution with bleaching ability used in the desilvering process of photosensitive materials contains red blood salt, red blood salt, and oxidizing agent for bleaching silver for one image.
Inorganic oxidizing agents such as dichromate were widely used.

However, some serious drawbacks have been pointed out to processing solutions containing these inorganic oxidizing agents that have bleaching ability. Although it is relatively good, it has unfavorable properties in terms of pollution prevention, as it may decompose when exposed to light and generate cyanide ions and hexavalent chromium ions that are harmful to the human body. Furthermore, treatment liquids containing these inorganic oxidizing agents have the disadvantage that it is difficult to reuse the waste liquid after treatment without discarding it.

On the other hand, oxidizing agents such as metal complex salts of arousal acids, such as aminopolycarboxylic acid metal complex salts, have been proposed as oxidizing agents that cause fewer pollution problems and meet the demands of speeding up and simplifying treatment, and enabling the reuse of waste liquids. In recent years, treatment solutions have come to be used. However, processing solutions using metal complex salts of organic acids have the disadvantage that the bleaching rate (oxidation rate) of the image silver (metallic silver) formed during the development process is slow due to its slow oxidizing power. 0 For example, iron ethylenediaminetetraacetate (iron ethylenediaminetetraacetate), which is considered to have a strong bleaching edge among aminopolycarboxylic acid metal complex salts,
III) Complex salts are used in some areas as bleaching solutions and bleach-fixing solutions, or in high-sensitivity silver halide color photographic materials based on silver bromide and silver iodobromide emulsions, especially as silver halide iodine. Photographic color paper, photographic color negative film, and color rehearsal film that contain silver oxide and have a high silver content have the disadvantage that bleaching blades are insufficient and the bleaching process takes a long time.

In addition, in development processing methods in which a large amount of photosensitive material is continuously processed using an automatic processor, etc., in order to avoid deterioration of the performance of the bleaching solution due to changes in the concentration of the components, it is necessary to keep the components of the processing solution within a constant concentration range. A means is necessary. In recent years, as such means, from the economic and pollution viewpoints, the so-called concentrated and low replenishment method, in which these replenishers are concentrated and refilled in small amounts, has been developed.
Another method has been proposed in which a regenerant is added to the overflow liquid and the overflow liquid is used again as a replenisher.

In particular, in a bleaching solution, an organic acid ferrous complex salt produced by bleaching developed silver, such as an ethylenediaminetetraacetate iron(n) complex salt, is aerated to produce an ethylenediaminetetraacetate iron(m) complex salt, that is, an organic acid ferric complex salt. A method has been put into practical use in which the liquid is oxidized back to water, a regenerating agent is added to supplement the missing components, and the liquid is used again as a replenisher.

However, in recent years, so-called compact laboratories (also known as mini-labs) have emerged in order to shorten the processing time of silver halide color photographic materials and reduce collection and delivery costs. There is a strong need to reduce the installation area of the machine, and recycling processing is not desirable because it requires complicated labor and management, and also requires processing space.

Therefore, it is preferable to use a concentrated low replenishment method that performs low replenishment without performing regeneration processing, but if the amount of replenishment of the bleaching solution is extremely reduced, the concentration of color developer components brought into the bleaching solution will increase.
In addition, it becomes more susceptible to the effects of concentration due to evaporation, and the accumulation of color developer components increases more and more. As described above, when the concentration of color developer components in the bleaching solution increases, the mixing ratio of reducing components such as color developing agents and sulfites increases, which inhibits the bleaching reaction and tends to cause failures called desilvering failures. Become. In order to improve these shortcomings, Research Disclosure JF-(Research Disclosure
) No. 24023 and the specific aminopolycarboxylic acid No. 2 described in JP-A No. 52-222252.
Techniques using iron complex salts and mixtures thereof have been proposed. However, it has been found that these techniques have various drawbacks.

For example, although the propylene diamine tetraacetic acid ferric complex salt described in the above-mentioned literature or patent publication has extremely strong oxidizing power, it is carried into the subsequently processed fixing solution or bleach-fixing solution by adhering to the photosensitive material. In this case, the fixing agent thiosulfate is decomposed and a so-called sulfidation phenomenon occurs.This drawback becomes more serious especially when the amount of replenishment of the fixing solution or bleach-fixing solution is reduced.

In addition, in recent years, there has been a trend in minilabs to use a waterless washing process (stabilization process) in which the amount of washing water is greatly reduced using specific chemicals, without the need for washing. There is a tendency for storage stability to become confusing.This tendency is becoming more and more emphasized in rapid processing in recent years.

[Objects of the Invention] Therefore, the first object of the present invention is to provide a method for processing a light-sensitive material, which is quick and has excellent storage stability of dye images, and further improves the occurrence of precipitation.

A second object of the present invention is to provide a method for processing photosensitive materials that has excellent processing stability and allows both continuous processing and small-scale processing over a long period of time.

[Structure of the Invention] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have developed a method for processing a photosensitive material in which, after color development, it is immediately processed with a bleaching solution, and then processed with a processing solution that has a fixing ability. In the method, the bleaching solution contains a ferric complex salt of a compound represented by the following formula [A], and the processing solution having fixing ability contains at least 0.0% of a sulfite or a sulfite-releasing compound.
It has been found that the above object can be achieved when the content is 1 mol/liter, and the present invention has been completed.

- Formula [A] [In the formula, At-A4 may be the same or different.
, -CHzOH, -GOON or PO3MIM2
wo table t.

M 1M+1M2 each represents a hydrogen atom, sodium, potassium or ammonium, X represents a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms, and the total number of carbon atoms including branched moieties is 3 or more. [Specific Structure of the Invention] The present invention provides that, when processing with a fixing solution or a bleach-fixing solution subsequent to bleaching, the bleaching solution contains a specific organic acid ferric complex salt, and the processing is continued. The desired effect of the present invention is achieved only when the fixing solution or bleach-fixing solution contains sulfite or a sulfite-releasing compound at a specific concentration or more, and the present invention may not be achieved even if any of these requirements is absent. do not have.

Next, the compound represented by the general formula [A] will be explained in detail.

A1-A4 may be the same or different, and -(
H20H, -COON or -P (represents hM+M2).

Ml and M2 each represent a hydrogen atom, sodium, potassium or ammonium, × is a substitution with 2 to 5 carbon atoms,
Unsubstituted fullkylene groups (e.g. ethylene, propylene,
butylene, pentamethylene, etc.), and the total number of carbon atoms including branched moieties is 3 or more. Substituents include hydroxyl group,
Examples include lower alkyl groups having 1 to 3 carbon atoms. less than,
Preferred specific examples of the compound represented by formula [A] above are shown below.

(A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (A-7) (A-8) These (A-1) to (A- For the compound 8), any sodium salt, potassium salt or ammonium salt thereof can be used in addition to the above.

From the viewpoint of the desired effects of the present invention, ammonium salts of these ferric complex salts are preferably used.

Among the above compound examples, those particularly preferably used in the present invention are (A-1), (A-2), (A-4),
(A-7), particularly preferred one is (A-7).
1).

The ferric chain salt of the compound represented by formula [A] is preferably used in an amount of 0.002 mol to 0.4 mol, more preferably 0.002 mol to 0.4 mol per 1 U of bleaching solution. The range is from 1 mol to 0.3 mol O, particularly preferably from 0.05 mol to 0.25 mol.

The bleaching solution of the present invention includes a ferric complex salt of the compound represented by formula [A] and other aminopolycarboxylic acid ferric complex salts.
Iron complex salts (e.g. ferric complex salts of ethylenediaminetetraacetic acid,
diethylenetriaminepentaacetic acid ferric complex salt, 1,2-cyclohexanediaminetetraacetic acid ferric chain salt, glycol ether diaminetetraacetic acid ferric complex salt, etc.). In particular, it is preferable to use it in combination with a ferric complex salt of ethylenediaminetetraacetic acid from the economic point of view and from the point of view of less bleaching fog.

The bleaching solution and/or bleach-fixing solution according to the present invention includes imidazole and its derivatives or the following formula [N to [IX]
When containing at least one of the compounds represented by
In the present invention, it is more preferably used.

General formula [1] [In the formula, Q represents an atomic group necessary to form a nitrogen-containing heterocycle (including those in which 5- to 6-membered unsaturated rings are condensed), and R is a hydrogen atom , an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic group (5 to 6
[General formula ■] [In the formula, R1 and R1 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxy group] , carboxy group,
Amino group, acyl group having 1 to 3 carbon atoms, aryl group,
Or represents an alkenyl group.

A represents an or 11-valent heterocyclic residue (including those in which 5- to G-membered unsaturated rings are condensed), and X is =S, =0, or =
NR''. Here, R and R' are synonymous with R1 and R3, respectively, X' is synonymous with X, and Z is a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, an alkyl Represents a group, or, R'+& hydrogen atom, alkyl group having 1 to 6 carbon atoms, cycloalkyl group, aryl group, heterocyclic residue (including fused 5- to 6-membered unsaturated rings) ) or an amino group, and nt to n6 and cloud, to -6 each represent an integer from 1 to 6.

are synonymous with R8 and R5, respectively. However, R4 and R5 may each represent -B-8Z, or R2
and R1, R and R', R, and R3 may be bonded to each other to form a ring.

Note that the compound represented by the chain formula also includes ethanolated products and salts thereof. J General formula [1[[] [wherein RIl and R7 are each 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, or an aryl group. group, alkenyl group or -B, -, Zl is a hydrogen atom,
Represents an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, or -S-B, -Y. R7 represents all integers from I to 6. ] General formula [IV] [In the formula, R8 and R1 represent each, and R1° is an alkyl method or -(cut)nsso
Represents 3e. (However, R1゜ is -(CHt)nas O3
When it is e, Q represents 0, and when it is an alkyl group, it represents l.

) Qe represents an anion. n represents an integer from 1 to 6.

]General Total V] [In the formula, Q represents an atomic group necessary to form a nitrogen-containing heterocycle (including those in which 5- to 6-membered unsaturated rings or saturated rings are condensed), R11 is a hydrogen atom, Q' is Q,
is synonymous with ] General formula [VI] [In the formula, D8, D*SDs and D4 each represent a simple bond, an alkylene group or vinylene group having 1 to 8 carbon atoms, and q3, ql, q, and q4 each represent 0
．． Represents 1 or 2. Further, the ring formed together with the sulfur atom may be further condensed with a 5- to 6-membered saturated or unsaturated ring. ] General formula [■] R+* R+s R+i [In the formula, Xx is 1000M', -H, -OH.

303M', C0NHt, 5OtNHt.

N H*, S H, CN, COt R+
s.

-9OtR+s, -0Rts, NR+aR+t.

SR0,5O3Rt*, NHCOR+a.

-N)ISO*R+s, 0CORts or -S
OtRls, Y represents R+s RIR+ or a hydrogen atom, - and n each represent 1 to 1O
represents an integer. R) + , RII * R+ 2 +
R+ 4 +R+s, rt+ and Ro each represent a hydrogen atom, a lower alkyl group, an acyl group, or a 1″ kyl group at i11 ■, and R1° is -N Rt.R1i-OR,!
Or +S R□, R1゜ and Rffil each represent a hydrogen atom or a lower alkyl group, and Ro represents R1
Represents the atomic group necessary to combine with 8 to form a ring.

Rye or R11 may be combined with R111 to form a ring. M' represents a hydrogen atom or a cation. ] General summary ■] (H)
B and B each represent a lower alkylene group, R13, R14, Rls and R1 each represent a hydroxy-substituted lower alkylene group, and X and y each represent 0 or I. G′ represents an anion;
2 represents 0, 1 or 2. ] General formula [IX] [In the formula, R38 and R:lo each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R1,
represents a hydrogen atom or an alkyl group, and R1 represents a hydrogen atom or a carboquino group. ] The compounds represented by the general formulas [1] to [IX] or imidazole and its derivatives used in the present invention are compounds generally used as bleach accelerators, and are hereinafter referred to as bleach accelerators of the present invention.

Typical specific examples of the bleach accelerators of the present invention represented by -Oga [I] to [IX] include, but are not limited to, the following.

Exemplary compound (1-1) (+-2)(
+-3) (1-4)(+-
5) (]-6)C)ItC)
ItCOOH (n-1) (II-2) (n-3) (II-4) (n-5) S S (II-6) H,N-C3NHNIIC3-NH.

(It-7) +t! lt-C5IIH(CHI)JIIC3-NH.

(n-8) (n-9) (Rho 10) (n-11) (n-12) (II-13) (II-14) (II-15) (n-16) (It-17) ( n-18) (It-19) υ (II-20) (n-21) (n-22) (II-24) (t[-25) (II-26) CU-27) (11-1) (Ill-
2)(III-3)C
m -4')(In-5) (
I[l-6) (I[[-7)
(I[l-8)(1') (
ILL-10) ([1-11) (III-12) (III-13) (I[l-14) ([1-15) (V-1) (V-2)(
V-3) (V-4)C)
I, 5CHIOH(
V-6) (V-7) (V-
8) (V-9) (V-1
0) (V-11)Hs (V-12) (V-13
)(V-14) (V-15) (V-16) (V-18) (V-19) (V-2
0) (V -21) (V -2
2) (V-23) H (V-24) (V-25) (V-26) (V-27) (V-28) (V-29) (V-30) (Vl-1) (Vl -2)
(Vl-1) (Vl-4) (V
I-5) (Vl-6) (Vl-7
) (Vl-8) (V
l-,9) (Vl-to) (Vl-
11) (Vl-12) (Vl-13)
(Vl -14) (■-15) 8υH (Vl-16) (Vl-17) (
■-1) (■-2) (■-3) (■-4) (■-5) (■-6) (■-7) (■-8) (■-9) (■-10) ( ■-11) (■-12) (■-13) H5CH20H2NCH2CH2GONH2H3 (■-14) HSCH2CH2NHCH2CH20)1 (■-15) )1scH2GHzNG)12G)120H (\layer-I
) CIl, N(C)ItCII, OB).

(■-2) (■-3) C11tN(CIL+CIIyOII).

(IX-1) (IX-2)'+1
8 (IX-3)
(IX-4) (IX-5
) The following margin imidazole and its derivatives A' -I A'-2A' -3A
'-4 A'-5A'-6 In addition to the bleaching accelerator of the present invention exemplified above,
Exemplary compound No., r-2, r-4 to 7.1-9 to 1 described on pages 51 to 115 of Specification No. 26:1568
3, l-16~21. l-23, ■-24, I-26
, 27, l-30 to 36, ■-38, ■-2 to 5, II
-7~IO,ll-12~20. ll-22~25.
ll-27゜ll-29~33, II-:15,35
,■-38~41. ll-43, 55 to ll-45,
■-57~60, ■-62~64, ■-67~71, ■
-73~79, ll-81~84, ■-86~99゜■
-101,102,ll-104~110,■-112
~119°H-121~124, ll-126, IT-
128-144. ll-146゜ll-148~15
5. ll-1571m-4, m-6~8゜m-10,
11, m-13, m-15~18, m-20゜■-2
2, ■-23, ■-25, ■-27, ■-29~32,
m-35, 36, IV-3, IV-4, V-3~6, V
-8 to 14, V-16 to 18, V-40 to 42, V-4
4-46, ■-48-66, ■-68-70, ■-72
~74, V-76~79, V-81, 82, V-84~
100. V-, 102~lO8, V-110, V-1
12,113, V-116~119, V-121~12
3. V-125~130, V-1: 12~144°V
-146~162. V-164-174. V-
176-184. 71-4, VT-7, Vl-10,
Vl-12, VT-13, Vl-16, Vl-19
, Vl-21, ■-22, ■-25, ■-27 to 34,
■-36, ■-3, ■-6, ■-13゜■-19, ■-
20 and the exemplary compounds (m-2) to (III
-3), (m-s) to (m-10), (III-12
) ~(m-45), (m-47) ~(m-so)
, (III-52) ~ (m-54), (m-56) ~ (
Compounds such as III-63) and (m-as) can also be used in the same manner.

These bleach accelerators may be used alone or in combination of two or more, and good results can generally be obtained when the amount added is in the range of about 00 to 100 g per liter of bleach-fix solution. However, in general, if the amount added is too small, the effect of promoting bleaching is small, and if the amount added is too large than necessary, precipitation may occur and cause contamination of the silver halide color photographic light-sensitive material being processed. Liquid per serving 0.05~
50 g is preferred, and more preferably 0.05 to ISg per 11 bleach-fix solutions.

When adding a bleaching accelerator, 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 methanol, ethanol, acetone, etc. as necessary. It can also be added after being dissolved in an organic solvent.

The processing temperature of the bleaching solution of the present invention is 20°C to 45°C, preferably 25°C to 42°C.

A halide such as ammonium bromide is usually added to the bleaching solution of the present invention.

The bleaching solution of the present invention includes various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. pH
Buffers may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained.

When the processing solution having fixing ability according to the present invention is a bleach-fix solution, the bleaching agent used in the bleach-fix solution is preferably a ferric complex salt of an aminocarboxylic acid or an aminophosphonic acid. Phosphonic acid represents an amino compound having at least two or more carboxylic acid groups and an amino compound having at least two or more phosphonic acid groups, respectively, and is preferably represented by the following general formula [X[1
] and [Xll1].

General formula [XI[] General formula [Xll In the formula, E represents a substituted or unsubstituted alkylene group, cycloalkylene group, phenylene group, Ra30RaJRa:+-1-RaiZR,3-, and Z is)N4a*-^ 6. ＞Represents N-As, R7
9 to R8 represent substituted or unsubstituted alkylene groups,
A, ~A6 are hydrogen atoms, -0■, -C:OOM, -PO
3M, where M represents a hydrogen atom or an alkali metal atom.

Next, preferred specific examples of the compounds represented by these general formulas [X[I] and [XIII] are listed below.

[Exemplary compounds] [X[[-1]ethylenediaminetetraacetic acid [XIr-
2] Diethylenetriaminepentaacetic acid [X[[-3]
Ethylenediamine-N-(β-hydroxyethyl)-N
, N'', N'-) diacetic acid [X[[-4]1.3-propylenediaminetetraacetic acid [XI[-5])diethylenetetraminehexaacetic acid [X
ll-6]cyclohexanediaminetetraacetic acid [X[[
-7]1,2-diaminopropanetetraacetic acid [X[[-
8] 1,3-diaminopropan-2-ol-tetraacetic acid [X[[-9]ethyl ether diamine tetraacetic acid [X
ll-10] Glycol ether diamine tetraacetic acid [XI [-11] Ethylene diamine tetrapropion [XI [-12] Phanylene diamine tetraacetic acid [X
I[-13]ethylenediaminetetraacetic acid disodium salt [XI[-14]ethylenediaminetetraacetic acid tetra(
trimethylammonium) salt [■-15] Ethylenediaminetetraacetic acid tetrasodium salt [■-18] Diethylenetriaminepentaacetic acid pentasodium salt [Xll-17] Ethylenediamine-N-(β-hydroxyethyl)-N, N', N'- ) cyclohexanediaminetetraacetic acid sodium salt [Xll-78]propylenediaminetetraacetic acid sodium salt [Xll-19]ethylenediaminetetramethylene phosphonic acid [X[[-201]cyclohexanediaminetetraacetic acid sodium salt [>1111-21]diethylenetriaminepentamethylenephosphonic acid Acid [X [[-22] Cyclohexanediaminetetramethylenephosphonic acid [Xl-1] Nitrilotriacetic acid [Xl-2] Methyliminodiacetic acid [)I-3] Hydroxiethyliminodiacetic acid [Xl-4]
] Nitrilotripropionic acid [Xl-5] Nitrotrimethylenephosponic acid [Xl-6] Iminodimethylenephosphonic acid [Xl-7] Hydroxyethyliminodimethyleneponphonic acid [Xl-8] Nitrilotriacetic acid trisodium salt These amino acids Among carboxylic acids and aminophosphonic acids, compounds particularly preferably used from the viewpoint of the desired effects of the present invention include 0Gl-t ), (X[[-2), (X[[-4
), (X[[-6), (Xll-7), (X[[-
10), (X[[-19), (XIIU-1), (X
lll-5).

Among these, (Xff-4) is particularly preferred from the viewpoint of the desired effects of the present invention.

The ferric complex salt of an organic acid according to the present invention is a free acid (hydrogen salt), an alkali metal salt such as a sodium salt, a potassium salt, a lithium salt, or an ammonium salt, or a water-soluble amine salt such as a triethanolamine salt. etc., but potassium salts, sodium salts and ammonium salts are preferably used. At least one of these ferric complex salts may be used, but 2a# and above can also be used together. The amount used can be arbitrarily selected and must be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed, but for example, 0.01 per IJL bleach-fix solution.
It can be used in a mole or more, preferably 0.05 to 1.0 mole. In addition, in the replenisher, it is desirable to use it in a highly concentrated form with the highest solubility in order to achieve low concentration and low replenishment.

The preferred replenishment amount of the bleaching solution according to the present invention is 20tJL to 50tJL per rn' of silver halide color photographic light-sensitive material.
hi, particularly preferably 30+*l to 3Sh
JL, more particularly preferably 40ral to 3
00mM, most preferably 5hJL to 25h
It is JL.

A so-called fixing agent is essential to the fixing solution and bleach-fixing solution according to the present invention.

As fixing agents, compounds which react with silver halides to form complex salts in aqueous solution, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate;
Examples include thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thiourea, and 1,000-onythyl.

In addition to these fixers, fixers and bleach-fixers include borax, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, hydroxide A single pH buffer agent or two or more types of pH buffers consisting of various salts such as ammonium may be included.

Furthermore, alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride,
It is desirable to contain large amounts of rehalogenating agents such as ammonium bromide, and PH buffering agents such as borates, oxalates, acetates, carbonates, phosphates, alkylamines, polyethylene oxides, etc. Those known to be added to fixing solutions and bleach-fixing solutions can be added as appropriate.

The fixing agent is used in an amount of 0.1 mol or more per processing liquid IJI, preferably in the range of 0.6 mol to 4 mol, particularly preferably 0.9 mol to 3.0 mol, from the viewpoint of the desired effect of the present invention.
The molar range is very particularly preferably between 1.1 mol and 2.1 mol.
It is used in a range of 0 mol.

In the present invention, in order to increase the activity of the bleach solution or bleach-fix solution, air or oxygen may be blown into the processing bath and processing replenisher storage tank as desired.
Alternatively, a suitable oxidizing agent 1 such as hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate.

When carrying out the method of the present invention, silver may be recovered from the fixer or bleach-fixer by known methods.

For example, the electrolysis method (described in the specification of Buddhist Patent No. 2,299,887), the precipitation method (described in JP-A-52-73037, the specification of Sec. Methods such as the method described in Japanese Patent No. 17114/1983 and the specification of Second Patent No. 2.548,237) and the metal substitution method (described in the specification of British Patent No. 1.35:1,805) can be effectively used.

It is particularly preferable to recover silver from the tank solution in-line, since the suitability for rapid processing becomes even better, but it is also possible to recover silver from the overflow waste solution and reuse it.

The fixing solution and bleach-fixing solution according to the present invention can better achieve the desired effects of the present invention when the replenishment amount thereof is 1100 c11 or less per 1 m'' of the photosensitive material.
2h to 650m sentences per rr', especially 30r
Remarkable effects are obtained for nl~400m sentences.

Furthermore, in the fixing solution and bleach-fixing solution according to the present invention, iodide (ammonium iodide, potassium iodide, sodium iodide, lithium iodide, etc.) is added at 0.1 g/fL to 10 g/fL! When L is contained, the effects of the present invention are further promoted. Especially (13
g/IL~5g/1. Particularly good results are obtained when the concentration is between 0.8 g/l and 2 g/l, most preferably between 0.8 g/l and 2 g/l.

When a compound represented by the following general formula [FA] or a compound of the following compound group [FB] is added to the processing liquid (fixer or bleach-fixer) having fixing ability according to the present invention, the present invention is applied. Not only does it achieve the desired effect better, but also
It is more preferably used in the present invention because it promotes the effect that very little sludge is generated when a small amount of light-sensitive material is processed over a long period of time using a fixing solution or a bleach-fixing solution.

(In the formula, R' and R' each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a nitrogen-containing heterocycle,
R' represents 2 or 3) Specific exemplary compounds represented by the general formula [FA] are shown below.

These compounds represented by -Oga [FA] are U.S. Patent No. 3
, 335,161 and U.S. Pat. No. 3.260.7.
It can be synthesized by a general method as described in the specification of No. 18.

Compound group [FB] FB-1 Thiourea FB-2 Ammonium iodide FB-3 Potassium iodide FB-4 Ammonium thiocyanate FB-5 Potassium thiocyanate FB-6 Sodium thiocyanate FB-7 Thiothia 7 Catechol These, the above- The compound represented by Oga [FA] and the compound of the compound group [FB] may be used alone,
It is also possible to use two or more types in combination.For example, thiourea, ammonium thiocyanate and ammonium iodide, thiourea and ammonium thiocyanate, (FA-12)
and thiourea, (FA-12) ammonium tothiocyanate, (FA-12) and ammonium iodide, (FA
-12) and (FA-32), (FA-12)
and (FA-38) are mentioned as preferred examples.

In addition, the amount of the compound represented by Oga [FA] and the compound of the compound group [FB] is Q, 1 per liter of treatment liquid.
Good results are obtained in the range of g to 200 g.

In particular, a range of 0.2 g to IQQg is preferable, and O, S
A range of g to SOg is particularly preferred.

9 tl of the bleaching solution of the present invention is used in a range of 2 to B, and from the viewpoint of the effects of the present invention, the pH is preferably in the range of 3 to 7, particularly preferably in the range of pH 4 to 6. Most preferably the ptl is in the range of 4.5 to 5.8.

The pH of the fixing solution and bleach-fixing solution used in the present invention is in the range of 4 to 8.

Sulfite and vi, m-releasing compounds according to the invention include potassium sulfite, sodium sulfite.

Ammonium sulfite, ammonium bisulfite.

Potassium bisulfite, sodium bisulfite, potassium metabisulfite, sodium metabisulfite.

Examples include ammonium metabisulfite. Furthermore, compounds represented by -Oga [B-1] or [B-2] below are also included.

General formula [B-1]! ... R,, -C-Of( SO,M General formula [B-2] In the formula, RI7 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R16 is an optionally substituted alkyl group having 1 to 5 carbon atoms; 1M is an alkali metal atom; R19, Rx; is a hydrogen atom or an optionally substituted alkyl group having 1 to 5 carbon atoms, and n is θ
Represents an integer of ~4.

Specific examples of the compounds shown above are described below, but the present invention is not limited thereto.

Preferred specific examples of the compounds represented by -Oga[B-13 and [8-21] are shown below.

B-1 Formaldehyde Sodium Bisulfite B-2 Acetaldehyde Sodium Bisulfite B-3 Propionaldehyde Sodium Bisulfite B-4 Butyraldehyde Sodium Bisulfite B-5 Succinic Aldehyde Sodium Bisulfite B-6 Glutaraldehyde Sodium Bisulfite B- 7β-Methylglutaraldehyde Sodium Bisulfite B-8 Maleic Dialdehyde Sodium Bisbisulfite These sulfites and sulfite-releasing compounds can be used in fixers or bleach-fixers 1! ; at least 0.1 as sulphite per liter
Moles are required, but 0.12 mol/state ~ 0.65 mol/! The range of L is preferably 0.15 moJl// 1 to 0
．． 50 mol/9. A range of 0.20 mol/1 to 0.40 mol/l is particularly preferred.

However, the number of moles of these sulfites and sulfite-releasing compounds are shown in values converted to sulfite.

The total processing time of the bleaching solution and the processing solution (fixing solution or bleach-fixing solution) having fixing ability according to the present invention is preferably 3 minutes 45 seconds or less, and the total time is more preferably 20 seconds to 3 minutes 20 seconds. The desired effects of the present invention are best achieved when the duration is particularly preferably from 40 seconds to 3 minutes, particularly preferably from 60 seconds to 2 minutes and 40 seconds.

Further, the deep mountain time can be arbitrarily selected within the above-mentioned total time range, but from the viewpoint of the desired effect of the present invention, it is preferably 1 minute 30 seconds or less, particularly 10 seconds to 70 seconds, especially 2 minutes or less.
The processing time of the processing liquid having a fixing ability, which is preferably 0 seconds to 55 seconds, can be arbitrarily selected within the above-mentioned total range, or is preferably 3 minutes and 10 seconds or less from the viewpoint of the desired effect of the present invention. It is preferably in the range of 10 seconds to 2 minutes and 40 seconds, particularly preferably in the range of 20 seconds to 2 minutes and 10 seconds.

In the processing method of the present invention, it is preferable to apply forced liquid stirring to the bleaching solution, the fixing solution, and the bleach-fixing solution. This is from the perspective of suitability.

The term "forced liquid stirring" as used herein means forcibly stirring the liquid by adding a means of agitation, rather than the usual diffusion movement of the liquid.

Examples of forced stirring means include the following methods.

1. High-pressure spray treatment method or spraying is a stirring method 2. Air bubbling treatment method 3. Ultrasonic oscillation treatment method 4. Vibration treatment method High-pressure spray treatment method is a discharge pressure of 0.1 kg/crn.
It refers to a method in which processing is carried out by directly spraying the processing liquid onto the photosensitive material from the spray nozzle under the following pressure. Spraying is a stirring method, and the discharge pressure Q from the nozzle is 1 kg.
/ cm' or more of pressure is applied to the processing solution directly into the processing solution,
This refers to a method of processing photosensitive materials by spraying them, and generally a pressure pump or a liquid pump is used as the pressure source. Pressurized bombs include plunger pumps, gear pumps, magnet pumps, and cascade pumps, such as the 15-LPM type, 10-BFM type, and 20-B manufactured by Maruyama Seisakusho.
FM type, 25-BFM type, etc. are known as examples.

In addition, as a liquid pump, for example, M[l-
Type 8, Myanmar [1-105, MD-20R type, Tou D-30R
Type, threshold D-55R type, MDK-2511, MDK-32
There is a type.

On the other hand, there are various types of nozzles and spray nozzles, such as a straight type, a fan type, a circular type, a full-face type, and a two-ring type. The impact force of the spray is mainly determined by the flow rate (1/ll1n) and the spray pressure (kg/crn'). Therefore, a pressurizing device is required that can adjust the pressure in proportion to the number of spray nozzles in order to fully exhibit the effect. The most preferable pressure is 0.3 to 10 kg/crn'; if the pressure is smaller than this, no effect can be obtained, and if it is too large, the photosensitive material may be scratched or damaged.

Next, in the air bubbling processing method, a sparger is installed at the bottom of the lower transport roller of the processing liquid tank, air or inert gas is sent to the sparger, and the air bubbles discharged from the sparger's mouth vibrate the photosensitive material. Furthermore, this is a method in which the processing liquid is brought into effective contact with the front, back, and side surfaces of the photosensitive material.

Suitable materials for the sparger include corrosion-resistant materials such as hard PVC, polyethylene-coated stainless steel, and sintered metal. 5■ to 15m5
You can get even better results if you do this. As a way to send air, you can use an air compressor, such as Bebicon (0.4K11.BU7TL) manufactured by Hitachi, Ltd.
7- Pump, e.g. Ehaiwaki Air Pump (Ap22)
Type 0), etc.

As an air basket, 2 sentences per rack conveyed by an automatic processor
301/win is required from win, 5M/ak
More favorable results are obtained from in to 20J1/win.

The amount of air or inert gas must be adjusted depending on the size of the processing liquid tank and the amount of photosensitive material. Preferably, an amount of active gas is delivered.

Next, the ultrasonic oscillation processing method is a method in which an ultrasonic oscillator is installed in the bottom or side wall space of the processing liquid tank of an automatic processor and irradiates ultrasonic waves onto the photosensitive material to increase the efficiency of development promotion. . aAs a sound wave oscillator.

For example, a magnetostrictive nickel vibrator (horn type), a magnetostrictive barium titanate vibrator (holder type), etc. manufactured by Ultrasound Kogyo Co., Ltd. are used.

The transducer frequency of the ultrasonic oscillator is 5 to 1000K.
Hz is used, but ultrasonic waves of 10 to 50 KHz are particularly preferable in terms of the desired effect of the present invention and damage to the equipment of automatic processors. Direct irradiation or indirect irradiation by providing a reflector may be used, but as the ultrasonic waves attenuate in proportion to the irradiation distance, direct irradiation is preferable, and the irradiation time should be at least 1 second. In the case of partial irradiation, it may be applied at any of the early, middle, and late stages of the treatment process.

Further, the vibration processing method is a method in which vibration is applied to the photosensitive material between the upper roller and the lower roller in the processing liquid tank of an automatic processor to effectively perform immersion processing. As the vibrator for the vibration source, for example, models V-28 and V-48 manufactured by Shindo Denki Co., Ltd. are generally used. The method of installing the vibrator is to fix the vibrator to the upper part of the immersion processing tank of an automatic processor, and install it so that the vibrator is applied from the back side of the photosensitive material. The frequency of the vibrator is 100 to 100
00 times/sin is preferable, and the most preferable range is 500 times/sin.
~6000 times/win. The amplitude of the photosensitive material to be processed is from 0.2+aa+ to 30mm, preferably l mrr
rw 20ou+. If it is lower than this, there is no effect;
Also, if it is too large, the photosensitive material may be damaged. The number of vibrators to be installed varies depending on the size of the automatic processor, but if the processing tank is composed of multiple tanks, a preferable effect can be obtained by installing at least one vibrator in each processing tank.

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

(1) Color development → bleaching → fixing → washing with water (2) color development → bleaching → fixing → washing → stabilization (3) color development → bleaching → fixing → stabilization (4) color development → bleaching → fixing → first stabilization → first stabilization 2 stable (5
) Color development → bleaching → bleach-fixing → washing (8) color development → bleaching → bleach-fixing → washing → stabilization (7) color development → bleaching → bleach-fixing → stable (8) color development → bleaching → bleach-fixing → first stabilization →Second stability Among these steps, especially (3), (4), (7),
(8) is preferred, particularly (3) and (4).

Another preferred embodiment of the processing method of the present invention is a method in which part or all of the overflow solution of the color developing solution according to the present invention is allowed to flow into the bleaching solution that is the next step. This is because when a certain amount of the color developing solution according to the present invention is introduced into the bleaching solution, the generation of sludge in the bleaching solution is improved.

The color developing solution according to the present invention includes alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium dihydroxide,
ammonium hydroxide, sodium carbonate, potassium carbonate,
It may contain sodium sulfate, sodium metaborate, borax, etc., and various additives such as benzyl alcohol, alkali metal silver halides, such as potassium bromide or potassium chloride, or development regulators such as citradinic acid. , hydroxylamine or sulfite may be contained as a preservative.

Furthermore, various antifoaming agents, surfactants, and organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide can be appropriately contained.

Further, the pH of the developer according to the present invention is usually 7 or more, preferably about 9-13.

The color developer used in the present invention may optionally contain antioxidants such as hydroxylamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose, or Hexose, pyrogallol-1,3
- Dimethyl ether etc. may be contained.

In addition, various chelating agents can be used in combination as metal ion sequestering agents in the color developing solution according to the present invention. For example, the chelating agents include ethylenediaminetetraacetic acid,
Aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, organic phosphonic acids such as l-hydroxyethylidene-1,1-diphosphonic acid, aminotri(methylenephosphonic acid)
or aminopolyphosphonic acid such as ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, phosphonocarboxylic acid such as 2-phosphonobutane-1,2,4-tricarboxylic acid, polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid. etc.

In the present invention, the desired effects of the present invention, especially the shelf life of dye images, are improved when processing with a stabilizer subsequent to a fixer or bleach-fixer.

The amount of replenishment of the stabilizer according to the present invention is 1 of the amount brought in from the pre-bath per unit area of color photographic light-sensitive material to be processed.
80 times, and preferably 2 to 60 times, but in the present invention, the concentration of the pre-bath component (bleach-fix solution or fixer) in the stabilizing solution is 1 to 1 in the final stabilizing solution tank. /
More preferably 500 or less, particularly preferably 1/1
000 or less.

Furthermore, from the viewpoint of low pollution and liquid storage stability, it is 1/500 ~
1/100000 is preferable, more preferably 1/100000.
The processing tank of the stabilization tank is configured to have a particle size of 2,000 to 1,150,000.

The stabilization treatment tank is preferably composed of a plurality of tanks, and the number of paddles is preferably 2 or more and Jl or less.

The effect of the present invention is when the stabilization treatment tank is 24g or more and 6 or less, and the countercurrent method (a method in which it is supplied to the rear bath and overflows from the front bath) is used.
In particular, it is preferable to use 2 to 3 tanks, more preferably 2 tanks, which is particularly preferable from the standpoint of reducing pollution and improving image preservation.

The amount brought in depends on the type of photosensitive material, the conveyance speed of the automatic processor,
Although it varies depending on the transportation method, squeezing method for the surface of the photosensitive material, etc., color photosensitive materials for photography usually use color film (
In the case of roll film), the usual carry-on amount is 50m1/
m''~150su/rn', and the replenishment amount at which the effect of the present invention on this carry-on amount is more remarkable is 50m
The range is 1/m'' to 4.0!L/rr1'', and the particularly effective replenishment amount is 200mJl/rr+' to 1500
119. /rr+' range.

The treatment temperature for the treatment with the stabilizing solution is preferably in the range of 15 to 60''C1, preferably 20 to 45C.

In addition, the stabilizer according to the present invention contains the following - Oga [■'
It is preferable to include chelating agents shown in ] to [■'] in order to improve whiteness in unexposed areas and prevent yellow staining of dye images after storage.

General formula [■'] (wherein, E is an alkylene group, a cycloalkylene group, a phenylene group, -R, -0-R5-1-Rs-0-Rs-0
-Rs- or -R5-Z-R8-, Z is >N-R
5-As and R each represent an alkylene group, A, -
Ayu represents -COOM or -PO,M, respectively,
A4 and As are hydrogen atoms, hydroxyl groups, -COOM, respectively
or -PO, l11. 6M represents a hydrogen atom or an alkali metal atom) General formula [VI''] (wherein, R1 is an alkyl group, a 7-aryl group, or a nitrogen-containing 6
0M representing a membered ring group represents a hydrogen atom or an alkali metal atom) General formula [■'] (In the formula, R8, R9 and RIG are a hydrogen atom, a hydroxyl group, -000)l, -P03M2 or an alkyl group, respectively. and Bl+B2 and R3 are each hydrogen atom, hydroxyl group, atom, alkyl group, -C2H40H or -P03M
2 represents a hydrogen atom or an alkali metal atom, and n and 1 represent 0 or 1, respectively.

Some specific examples of chelating agents represented by the general formulas [■'], [vN'], and [IX"l are shown below. The chelating agents used in the present invention are not limited to the specific examples below. .

[Exemplary chelating agent] C1l.

CH,C00II N←CH, PO mountain 'CHtPOaHt OH OH1 HtOcoP-CPOJ* P.O.”

0sHt HOCCH2 Coo)l 0sl12 110-C11 HOOCCH* 0sllt 1O-C-11 1100C-C-11 P.O., II.

PO, HL 1O-C-COOH ■ H-C-Cool PO, HL 1C-cooH HC-COOH 0sHt CI t C0OH CH-C0OH CH-Coo)1 0sHt CI, COO11 CH.

HOOCC,H,-C-COO11 P.O., H.

C) It call " 1100C-C-PO, II.

CH.

CIl, COOH CHtCOOH CBCII, Cool ■ CIIPOJ* 0Jt CIl, C0OH Ht C, +1. -C-PG,H.

straight CIl　C0OH CM　CfHs ■ 1100c -C-C0OH ■ C1bPO3)1t C1, COO11 CHCH.

Cl-COO11 POriH! co, coon HCOOH ■ C,H・-C-COO11 0sllt C1, PO3H.

/ Pso CHtPOsH will ’　CHtPO,H* C1bPO311t H,0koP-C-PO311゜ ■ 0 ■ CH,OH )1,03P-C-PO51lt OH OH H,0sP-C-PO3)1t OH1 CH2 PO, 11° CHtPOsH* ζ CH-Cool CH,C00H CHt-C0OH C.I.

++00C-C-POs H.

CH.

C) I I C00H OHOHOH The chelating agent preferably used in the above stabilizing solution is preferably used in an amount of 0.01 to 100 g, more preferably 0.05 to 50 g, and particularly preferably 0.1 g, per 11 stabilizing solutions. ~20g.

In addition to the effects of the present invention, the pH value of the stabilizer preferably used in the present invention is P)! for the purpose of improving image storage stability. The range of 4.0 to 9.0 is preferable.

More preferably the pH is in the range of 4.5 to 9.0, particularly preferably the pH is in the range of 5.0 to 8.5.

As the pH adjuster that can be contained in the stabilizer preferably used in the present invention, any commonly known alkaline agents or acid agents can be used.

Stabilizing liquids preferably used in the present invention include organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.),
pH adjuster (phosphate, borate, hydrochloric acid, fE acetate), surfactant, preservative, Bi, Mg, Zn, old, A
Metal salts such as I, Sn, Ti, Zr, etc. can be added. The amount of these compounds to be added is necessary to maintain the pH of the stabilizing bath according to the present invention, and in any combination, the amount is within the range that does not adversely affect the stability of color photographic images during storage and the occurrence of precipitation. I don't mind.

Anti-spill agents preferably used in the stabilizer of the present invention include hydroxybenzoic acid ester compounds, phenolic compounds,
Thiazole compounds, lysine compounds, guanidine compounds, carbamate compounds, morpholine compounds,
These include quaternary phosphonium compounds, ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, amino acid compounds, active halogen-releasing compounds, and penttriazole compounds.

The hydroxybenzoic acid ester compound includes methyl ester, ethyl ester, propyl ester, butyl ester, etc. of hydroxybenzoic acid, preferably n-butyl ester, isobutyl ester, propyl ester of hydroxybenzoic acid, and more preferably This is a mixture of three types of hydroxybenzoic acid esters.

The phenolic compound preferably used as the anti-spill agent of the present invention is a compound which may have an alkyl group, a halogen atom, a nitro group, a hydroxyl group, a carboxylic acid group, an amino group, a phenyl group, etc. as a substituent, and is preferably a compound. are ortho phenylphenol and orthocyclohexyphenol,
Phenol, nitrophenol, chlorophenol.

These are cresol, guaiacol, and aminophenol.

Particularly preferably, the combination with a bisulfite adduct of ortho-phenylphenol or an aldehyde derivative exhibits remarkable anti-puff properties.

The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, and is preferably 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiacylindone, or 2-octyl-4-isothiazoline. 3-on,
Tochlor 2-methyl-4-isothiazolin 3-one,
2-chloro-4-thiazolyl-penzimidazole.

Specifically, pyridine compounds include 2,6-dimethylpyridine, 2,4,8-)limethylpyridine, radium-2
-Pyridinethiol-1-oxide, etc., but preferably radium-2-pyridinethiol-! -It is an oxide.

Specifically, guanidine compounds include cyclohexidine,
Examples include polyhexamethylene biguanidine hydrochloride, dodecylguanidine hydrochloride, etc., and dodecylguanidine and its salts are preferred.

Specific examples of carbamate compounds include methyl-1-(butylcarbamoyl)-2-benzimidazole carbamate and methylimidazole carbamate.

Specific examples of morpholine compounds include 4-(2-nitrobutyl)morpholine and 4-(3-nitrobutyl)morpholine.

Quaternary phosphonium compounds include tetrafurkylphosphonium salts, tetraalkoxyphosphonium salts, etc.
Preferred are tetraalkylphosphonium salts, and more specific preferred compounds are tri-n-butyl-tetradecylphosphonium chloride and triphenyl-nitrophenylphosphonium chloride.

Specific examples of quaternary ammonium compounds include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, alkylpyridium salts, and specific examples include dodecyldimethylbenzylammonium chloride, dodecyldimethylammonium chloride, and laurylpyridinium chloride. etc.

Specifically, urea-based compounds include N-(3,4-dichlorophenyl)-N'-(4-chlorophenyl)urea, N-(
Examples include 3-)lifluoromethyl)-N''-(4-chlorophenyl)urea.

Specific examples of inxazole compounds include 3-hydroxy-5-methyl-isoxazole.

Propatool 7mino compounds are n-7' a ha7-
There are tools and impromptu tools, specifically 0L-2.
-benzylamino-1-propanol, 3-diethylamino-1-propanol, 2-dimethylamino-2-methyl-1-propanol, 3-amino-1-propanol, idopropanolamine, diisopropanol Examples include amine, N,N-dimethyl-isopropanolamine, and the like.

Examples of sulfamide compounds include 0-nitrobenzenesulfamide, p-aminobenzenesulfamide, 4-chloro-3,5-dinitrobenzenesulfamide, and α-amino-p-toluenesulfamide.

A specific example of the amino acid compound is trauryl-β-alanine.

Active halogen-releasing compounds include primary sodium hypochlorite, dichloroisocyanurate chloramine T, chloramine B, dichlorodimethylhydantoin, and chlorobromodimethylhydantoin, while primary sodium hypochlorite, sodium dichloroisocyanurate, trichloroisocyanurate Acids are preferred.

Specific examples of penttriazole compounds include the following.

(a) Penztriazole (b) Among the above anti-spill agents, compounds preferably used in the present invention include phenolic compounds, thiazole compounds, pyridine compounds, guanidine compounds, quaternary ammonium compounds, and active halogen-releasing compounds. , a penztriazole compound. Furthermore, from the viewpoint of liquid storage properties, phenolic compounds, thiazole compounds,
These are active halogen-releasing compounds and penztriazole compounds.

If the amount of the anti-pie agent added to the stabilizer is less than 0.001 g per liter of the stabilizer, the desired effect of the present invention will not be achieved, and if the amount exceeds 50 g, it will be unfavorable in terms of cost, and the preservation of the dye image will be impaired. 0.0 because the stability deteriorates on the contrary.
Used in the range of 01 to 50g, preferably o, oos
It is used in the range of ~1 Gg.

In the processing of the present invention, silver may be recovered by various methods from processing solutions containing soluble silver salts, such as fixing solutions and bleach-fixing solutions as well as stabilizing solutions. 667 specification), precipitation method (Japanese Patent Application Laid-open No. 5
Described in Publication No. 2-73037.

West German Patent No. 2,331,220 (described by JIL), ion exchange method (described in JP-A-51-17114, Second Patent No. 2,548,237), and metal substitution method (British Patent No. 1, 353,805) etc. can be effectively used.

Furthermore, when recovering silver, the soluble silver salt is recovered from the overflow solution of the processing solution, and the silver is recovered by the method described above.

The remaining liquid can be disposed of as waste liquid, or a regenerating agent can be added.
It is particularly preferred to mix a stabilizing solution, which may be used as a replenisher or bath processing solution, with a fixer or bleach-fixer prior to silver recovery.

In addition, 1 treatment of bringing the stabilizer of the present invention into contact with an ion exchange resin, electrodialysis treatment (see Japanese Patent Application No. 511-96352)
or reverse osmosis treatment (see Japanese Patent Application No. 59-98532).

In addition, it is preferable to use water that has been previously deionized in the stabilizing solution of the present invention, since this improves the anti-piping properties of the stabilizing solution, the stability of the stabilizing solution, and the image storage stability. As a means of deionization treatment, the dielectric constant of the rinse water after treatment is 507 L*/cm or less.

or Ca, >1g Any material may be used as long as it reduces ions to below the spp level.1 For example, it is preferable to use an ion exchange resin or reverse osmosis membrane for treatment alone or in combination.For ion exchange resins and reverse osmosis membranes, Public technical report 8
Although described in detail in No. 7-1984, it is preferable to use a strongly acidic H-type cation exchange resin and a strongly basic OH-type anion exchange resin.

In the present invention, the salt concentration in the stabilizing solution is 11,000 ppm or less, preferably 800 ppm or less, which enhances the washing effect and is good for improving the white background and preventing pimples.

The processing time for the stabilizing solution in the present invention is 2 minutes or less, preferably 1 minute and 30 seconds or less, particularly preferably 1 minute or less in order to achieve the effects of the present invention, particularly for the processing stabilizing solution.

In the method for processing a silver halide color photographic material of the present invention, the average silver iodide content of all the silver halide emulsions in the silver halide photographic material is preferably 0.1 to 15 mol%, More preferably, it is 0.5 to 12 mol %, particularly preferably 1 to 6 mol %.

In the method for processing a silver halide color photographic material of the present invention, the average grain size of all the silver halide emulsions in the silver halide color photographic material is preferably 2.0 #L or less, more preferably 0.1 to 1. The OIL is less than ■, particularly preferably 0.2 to 0.6 μ■.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, the total dry film thickness of all the woody colloid layers of the silver halide color photographic light-sensitive material (hereinafter referred to as the film thickness on the emulsion side)
The lower limit of is determined by the silver halide emulsion, coupler, oil agent, additives, etc. contained, and the preferred film thickness on the emulsion surface is 5 to 18 ILm, more preferably 1O to 16.
It is a temple.

Also, the distance from the outermost surface of the emulsion surface to the lower end of the emulsion layer closest to the support is preferably 144 square meters or less, and the distance from the emulsion layer to the lower end of the emulsion layer that is the next closest to the support is preferably 144 cm or less. 1
0IL or less is preferable.

The photosensitive material according to the present invention uses an internal development method (U.S. Pat. No. 2,376,679) in which a coupler is contained in the photosensitive material.
No. 2,801,171), and any couplers generally known in the art can be used.For example, cyan couplers are based on naphthol or phenol structures, and indoaniline For example, magenta couplers include those having a 5-pyrazolone ring having an active methylene group as a skeleton structure and pyrazoloazole type ones, and yellow couplers include those having an active methylene ring. benzoylacetanilide, bivalylacetanilide, and those having an acylacedoanilite structure, with or without a substituent at the coupling position, can be used. In this way, as the coupler, both a so-called 2-equivalent type coupler and a 4-equivalent type coupler can be applied.

Hereinafter, couplers preferably used in the present invention will be explained in detail.

As a cyan coupler, the following formula [C-Al, [C-
B] and [C-C].

- Formula [C-A] OH General formula [C-B] OH (wherein, R1 represents an alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group, and Y is a group represented by Yes (However, R2 represents an alkyl group, alkenyl group, cycloalkyl group, aryl group, or heterocyclic group, and R3 represents a hydrogen atom or a group represented by R2. R2 and R1 may be the same or different. , may be combined with each other to form a 5- to 6-membered heterocycle), 2
represents a hydrogen atom or a vine group that is separated by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent.)
-Formula [C-C] R3 is -CONR, R1, -NHCOR, -NIIG
OOR6, -NH3O,R,, -N)IcONRJs or -NH3O□NR,11,, R2 is a monovalent group, R1 is a substituent, X is a hydrogen atom or reaction with an oxidized aromatic primary amine developing agent a group that leaves by, intersection is 0 or l, - is 0 to 3, R,, Rs is a hydrogen atom, aromatic group, aliphatic group, or heterocyclic group, R6 is an aromatic group, aliphatic group, or heterocyclic group Each represents a group, and when Satsu is 2 or 3, each R and I may be the same or different, or may be combined with each other to form a ring,
Also, R4 and Rs, Re and R3゜R2 and
CONHR, and R7 represents an aromatic group.

First, the above-mentioned -mathematical formula [C-A] and -mathematical formula [CB] will be explained. In the chain formula, Y is.

It is a group represented by Here, R1 and R o are each an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (e.g., methyl, ethyl, t-butyl, dodecyl, etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms. (
allyl group, heptadecenyl group, etc.), cycloalkyl group,
Preferably 5- to 7-membered rings (e.g., cyclohexyl, etc.), aryl groups (e.g., phenyl, tolyl, naphthyl, etc.), heterocyclic groups, preferably containing 1 to 4 nitrogen, oxygen, or sulfur atoms. Represents a 5- to 6-membered cyclic group (e.g., furyl group, thienyl group, benzothiazolyl group, etc.), R represents a hydrogen atom or a group represented by R1, and R2 and 6 are bonded to each other to form a 5- to 6-membered ring group. A heterocycle may be formed. Furthermore, any substituent can be introduced into R1 and R3. For example, an alkyl group having 1 to 10 carbon atoms (e.g. methyl, toprobyl, i-butyl, t-butyl) .

t-octyl, etc.), aryl groups (e.g. phenyl, naphthyl, etc.), halogen atoms (fluorine, chlorine, bromine, etc.), cyano, nitro, sulfonamide groups (e.g. methanesulfonamide, butanesulfonamide, p-toluenesulfonamide, etc.) ), sulfamoyl group (methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl group (e.g. methanesulfonyl, p-toluenesulfonyl, etc.), fluorosulfonyl group, carbamoyl group (e.g. dimethylcarbamoyl, phenylcarbamoyl, etc.), oxycarbonyl group (e.g. ethoxycarbonyl, phenoxycarbonyl, etc.), acyl groups (e.g. acetyl, benzoyl, etc.), heterocycles (e.g. pyridyl group, pyrazolyl group, etc.),
Examples include an alkoxy group, an aryloxy group, an acyloxy group, and the like.

In the general formula [C-Al and - formula [C-B1, R
, preferably represents a ballast group necessary for imparting diffusion resistance to the cyan coupler represented by the formula [C-Al and the formula [C-B] and the cyan dye formed from the cyan coupler. An alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group having 4 to 30 carbon atoms.
-butyl, n-octyl, t-octyl, n-dodecyl, etc.), 5-membered or 6-membered heterocyclic groups, and the like.

In the general formula [C-Al and formula [C-B1], 2 represents a hydrogen atom or a group that can be separated during the coupling reaction with the oxidized product of the N-hydroxyalkyl-substituted p-phenylenediamine derivative color developing agent 0 For example: , halogen atoms (e.g. chlorine, bromine, fluorine, etc.), i! substituted or unsubstituted alkoxy groups, aryloxy groups, heterocyclic oxy groups,
Examples include acyloxy group, carbamoyloxy group, sulfonyloxy group, alkylthio group, arylthio group, heterocyclic thio group, sulfonamide group, and more specific examples include U.S. Pat. −
No. 37425, Japanese Patent Publication No. 4B-36894, Japanese Patent Publication No. 1973
-10135, 50-117422, 50-1
No. 30441, No. 51-108841, No. 50120
No. 343, No. 52-18315, No. 53-10522
No. 6, No. 54-14736, No. 54-48237,
No. 55-32071, No. 55-65957, No. 56
-1938, 56-12643, 56-271
No. 47, No. 59-146050, No. 59-16695
No. 6, No. 60-37557, No. 60-35731,
In the present invention, cyan couplers represented by the general formula [C-Dl are preferred.

General formula [C-Dl H In the general formula [C-Dl, R4 is a substituted or unsubstituted aryl group (especially preferably a phenyl group). When the aryl group has a substituent, the substituent is - 3O2
R,, halogen atom (fluorine, chlorine bromine, etc.), -CF
3. -No□, -CN, -COR,.

-COOR%, -3o□ORs, At least one substituent selected from is included.

Here, R5 is an alkyl group, preferably having 1 to 20 carbon atoms.
an alkyl group (e.g. methyl, ethyl, 1-butyl, dodecyl, etc.), an alkenyl group preferably having 2 to 2 carbon atoms.
20 alkenyl groups (allyl group, heptadecenyl group, etc.)
, represents a cycloalkyl group, preferably a 5- to 7-membered ring (e.g., cyclohexyl, etc.), an aryl group (e.g., phenyl group, tolyl group, naphthyl group, etc.), and R6 is a hydrogen atom or a group represented by R, be.

In a preferred compound of the cyan coupler of the present invention represented by the general formula [C-Dl, R4 is a substituted or unsubstituted phenyl group, and the substituent to the phenyl group is cyano, nitro,
-3O, R, (R is an alkyl group) halogen atom, and trifluoromethyl.

In the general formula [C-Dl, 2 and R are each - formula [C
-Al and [C-B1 have the same meaning. R1
A preferred example of the ballast group represented by the following formula [
It is a group represented by C-El.

General formula [C-El In the formula, J represents an oxygen atom, a sulfur atom, or a sulfonyl group, K represents an integer from θ to 4, and 0 or 1 is present when K is 2 or more. R9 may be the same or different, Ra represents a linear or branched carbon fi1-20 chain, and a substituted alkylene group such as an aryl group;
g represents a monovalent group, preferably a hydrogen atom, a halogen atom (e.g. chromium, bromine), an alkyl group, preferably a linear or branched alkyl group having 1 to 20 carbon atoms (e.g. methyl, t-butyl, t-butyl, - 6 groups such as pentyl, t-octyl, dodecyl, pentadecyl, benzyl, phenethyl)
, an aryl group (e.g. phenyl group), a heterocyclic group (e.g. a thiogen-containing heterocyclic group), an alkoxy group, preferably a linear or branched alkoxy group having 1 to 20 carbon atoms (e.g. methoxy, ethoxy, t-butyloxy, octyl oxy, decyloxy, dodecyloxy, etc.), aryloxy group (e.g. phenoxy group), hydroxy group, acyloxy group, preferably alkylcarbonyloxy group, arylcarbonyloxy group (e.g. acetoxy group, benzoyloxy group), carboxy, Alkyloxycarbonyl group, preferably a straight chain or branched alkylcarbonyl group having 1 to 20 carbon atoms, preferably phenoxycarbonyl group, alkylthio group, preferably acyl group having 1 to 20 carbon atoms, preferably acyl group having 1 to 20 carbon atoms. Straight chain or branched alkylcarbonyl group, acylamino group, preferably straight chain or branched alkylcarboxamide group having 1 to 20 carbon atoms, benzenecarboxamide group, sulfonamide group, preferably straight chain or branched chain having 1 to 20 carbon atoms. Branched alkylsulfonamide group or benzenesulfonamide group, carbamoyl group,
Preferably a linear or branched alkylaminocarbonyl group or phenylaminocarbonyl group having 1 to 20 carbon atoms, a sulfamoyl group, preferably a linear or branched alkylaminosulfonyl group or phenylaminosulfonyl group having 1 to 20 carbon atoms, etc. .

Next, specific examples of compounds of the cyan coupler of the present invention represented by the general formula [C-A] or [C-8] will be shown, but the invention is not limited thereto.

[Exemplary compounds]

(1)♀11 H OH CHl OH 0■ Oh.

H 0H OH (t) CI, □ OH OH OH Oh.

σ-25 t 4H9 OH OH C4H@ 07. □ C-83 0 bar 04H9 t n! H 068! .

0g H 0 days H H C-45 u (t) C4H.

H Next, the general formula [C-Cl will be explained.

The six groups represented by R2-R7 in the general formula [C-C1 include those having substituents.

R6 is an aliphatic group having 1 to 30 carbon atoms, and 6 to 3 carbon atoms;
An aromatic group having 0 carbon atoms and a heterocyclic group having 61 to 30 carbon atoms are preferable, and R4, R, and the like are preferably hydrogen atoms, and Rr and the like are preferably mentioned as preferable groups.

Directly or N) 1. Hydrogen atom bonded to NH via Go or S02, aliphatic group having 1 to 30 carbon atoms, aromatic group having 6 to 30 carbon atoms, heterocyclic group having 1 to 30 carbon atoms, -OR,, -COR .

-PO+OR+ola, -PO-+RIO)2,
-CO2RIO1-3O,R,.

or -3O2ORto (Ra, R9 and RIG are the same as defined for R4, R8 and R6 above, respectively, and R8 and R9 may be combined to form a heterocycle) is preferred.

R7 is preferably an aromatic group having 6 to 30 carbon atoms,
A typical example of the substituent for R7 is a halogen atom.

Hydroxy group, amino group, carboxyl group, sulfonic acid group, cyano group, aromatic group, heterocyclic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group, imide group, aliphatic group, aliphatic oxycarbonyl group, etc. can be mentioned. When substituted with a plurality of substituents, the plurality of substituents may be bonded to each other to form a ring, such as a dioxymethylene group.

Representative examples of R3 include a halogen atom, a hydroxy group, an amino group, a carboxyl group, and a sulfonic acid group.

Cyano group, aromatic group, heterocyclic group, carbonamide group,
Sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group,
Aliphatic sulfonyl group.

Examples include an aromatic sulfonyl group, a sulfamoylamino group, a nitro group, an imide group, etc., and the number of carbon atoms contained in R1 is preferably 0 to 30. When s=2, a cyclic R
Examples of 3 include dioxymethylene groups and the like.

When the sentence is 1, R1 is particularly preferably -CONRJs,
(2) is preferably 0, and R2 is C0Ra directly bonded to NH.
, -C00Rno, -! lio,R,,-CONRa
Rs, -3O,NRaR.

is particularly preferred, and more preferred are -COOR+o, -coRa, and -3OtR+o, which bond directly to 11cNH, and among them, -COOR,,, is most preferred.

Also included in the present invention are those that form dimers or more multimers via R1 to R3 and X.

Among the general formula [C-CF, the case where intersection=0 is preferred.

Specific examples of couplers represented by the general formula [C-CF are JP-A Nos. 60-237448, 61-153640, and 6
No. 1-145557, No. 62-85242, No. 4g-
No. 15529, No. 50-117422, No. 52-18
No. 315, No. 52-90932, No. 53-52423
No. 54-48237, No. 54-65129, No. 55-42071, No. 55-65957, No. 55-
No. 105226, No. 56-19:18, No. 56-12
No. 643, No. 56-27147, No. 56-12683
No. 2, 58-95:146 and U.S. Patent Co., 488.
, No. 193, etc., and can be synthesized by the methods described therein.

To add a coupler to a photosensitive material, depending on the physical properties (for example, solubility) of the coupler, an oil-in-water emulsion dispersion method using a water-insoluble high-boiling organic solvent, or an alkaline dispersion method in which the coupler is added as an alkaline solution are used.

Various methods can be used, such as a latex dispersion method and a solid dispersion method in which fine solids are directly added.

The amount of coupler added is usually per mole of silver halide.1.
OX 10-3 mol to 1.0 mol, preferably 5.0 mol
The range is from 3 moles to a, ox to -' moles.

Next, typical examples of the coupler represented by the general formula [CC] will be shown, but the present invention is not limited thereto.

[Exemplary Compound] CI13CON11 CIlsSOJH C,F? C0NHCQ CH L(i)C3Ht] JSOtNll CH 0■ CH,SO,NII 0CHtCHtSOJaCzl
lsOCON)l C-63 C-64 H C, Il, 0CONII C1゜Il, , 0CONH CH30CONHCQ H (+)C411eOcONH CIl. SO, NH C4H. OCONH 1115 sushi υ+1i C-75 0) 1 (C.H,O), PNH 0H c-g.

CtllsOCONII x : y -60: 40 (molar ratio) N

Nu
0th ;CIIy
CHtSCHtCHtCOrHCO, H C1, CHJHSO, CII CH, CH, 5C1lC, *II□ ■ Otn 0CIltCOOH NIICOC112CIitCOtllCIlII+3 C1lC1, C-Cl, + I Cl1. C.I.

0 (CH friend) *C00H C+ tH 5 C,,+1. .

OOH OOH ool 0OII oon CO,H (Molar ratio) The silver halide emulsion that can be used in the present invention is preferably a tabular silver halide emulsion, but in addition to this,
Any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide may be used; As the protective colloid for silver halide, in addition to natural products such as gelatin, various products obtained by synthesis can be used. The silver halide emulsion may contain conventional photographic additives such as stabilizers, sensitizers, hardeners, sensitizing dyes, and surfactants.

As the photosensitive material used in the present invention, color negative film, color paper, color reversal film, color reversal paper, etc. can all be used.

[Effects of the Invention] According to the present invention, silver bleaching properties are improved, processing stability is excellent, and dye image storage stability is improved in rapid processing in which color development is followed by bleaching and fixing processing. .

[Example] Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 In all Examples, the amount added in the silver halide photographic light-sensitive material is expressed in g per lrn' unless otherwise specified, and silver halide and colloidal silver are expressed in terms of silver. .

Sample 1 of a multilayer color photographic material was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

Sample 1 (comparison) 1st layer: Antihalation layer (IIG-1) Black colloidal silver...0.22 Ultraviolet absorber (UV-1
) -0,20 colored coupler (C (knee 1)
...0.05 colored coupler ((:M-2)
-...0.05 high boiling point solvent (oil-1)"
...0.20 gelatin ...1,4 second layer: intermediate layer (IL-1) ultraviolet absorber (UV-1) -0, former high boiling point solvent (oil-1) = -0,01 gelatin
・-1,4 3rd layer: Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (E, -1) ...1.0 Silver iodobromide emulsion (E, -2) ・-0, 5 sensitizing dye (S-
1) ...2.5 Xl0-'(mol/#1
Sensitizing dye (S-2)...2.5 Xl0-
'(mol 1 silver 1 mol) Sensitizing dye (S-3)...-0,5xlO-'
(mol l silver l dry) Cyan coupler (C-4) ...1.2 cyan coupler (c-z) -o, oa colored cyan coupler (CG-1) ... -O,0S DIR compound (D -1) -0,002 high boiling point solvent (oil-1)...0.5 gelatin
...1.4 Fourth layer: High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (E, -3) -2,0 sensitizing dye (S-1) ...2. OXl0-' (mol l
1 mole of silver) Sensitizing dye (S-2)...2. OxlO-'
(Mole/1 mole of silver) Sensitizing dye (S-3)...0. I Xl0-
'(dried ring/silver 1 mole) Cyan coupler (C-1) ...0.15 cyan coupler (C-2) ...0.018 cyan coupler (C-3) -1, IS colored cyan Coupler (CC-1)...0.015 DIR compound (D-2)...0.05 High boiling point solvent (of +-1) -0.5 Gelatin
...1.4 5th layer: Intermediate layer (IL-2
) Gelatin...0.5 6th layer: Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (E,,-1)...1.0 Sensitizing dye (S-4)... 5. [l x 10-
'(mol 1 silver 1 mol) Sensitizing dye (S-5)... Bow, OXl 0-4 (
mol/1 mol of silver) Magenta coupler (Tol)...0.5 Colored magenta coupler (CM-1)...0.05 DIR compound (It-3)...0.015
DIR compound CD-4) ・0.020 High boiling point solvent (oil-2) ・・・0.5 Gelatin
... Bow, 0 7th layer: Intermediate layer (IL-3) Gelatin ...0.8 High boiling point solvent (o
il-1) = 0.2 8th layer: High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Ea-3) ...1.3 Sensitizing dye (s-e) ...1 .5 Xl0-4 (mol l silver l moh) Sensitizing dye (S-7)...2.5 Xl0-
4 (mol/silver 1 mol) Sensitizing dye (S-a)...0.5 Xl0-
4 (mol/1 mole of silver) Magenta coupler (G2)...0.06 Magenta coupler (G3)...0.18 Colored magenta coupler (C)! -2)...0.05 111R compound (D-3)...0.01 High clear point solvent (oil-3)...0.5 Gelatin...Archie, O 9th layer: Yellow filter layer ( YC:) Yellow colloidal silver...0.1 color stain inhibitor (SC-1)
...0.1 high clear point solvent (oil-3)
...-0,1 gelatin ...0.8 10th layer: low-speed blue-sensitive emulsion layer (BL) silver iodobromide emulsion (E
a-1) ...0.25 silver iodobromide emulsion (El-
2) ...0.25 sensitizing dye (S-10)
...7. OXl0-' (mol/silver 1 mol) Yellow coupler (Y-1)...0.6 Yellow coupler (Y-2)...0.12DIR compound (
D-2) ...0.01 high boiling point solvent (oil
-3) ...0.15 gelatin
...1.0 11th layer: High sensitivity blue sensitive emulsion layer (BH)
Silver iodobromide emulsion (El-4) ...0.50 Silver iodobromide emulsion (Es-1) ...0.20 Sensitizing dye (S-9) -1, OXl0-4 (Morno silver 1
Mol) Sensitizing dye (S-10) ・3. OXl0-4(
Moh/1 mole of silver) Yellow coupler (Y-1)...0.38 Yellow coupler (Y-2)...0. OB high boiling point solvent (
oil-3) ...0.07 gelatin
...1.1 12th layer: first protective layer (Pro-
1) Fine grain silver iodobromide emulsion...0.4 (average grain size 0.4)
08JLII, Ag12 mol%) ultraviolet absorber (UV
-1) ・0.10 ultraviolet absorber (UV-2)
-0.05 high boiling point solvent (oil-1) ・
・0.1 High boiling point solvent (oil-4) ・=0.1
Formalin scavenger-01S-1)...0.5 Formalin scavenger ()Is-2)...0.2 Gelatin...1.0 13th layer: 2nd
Protective layer (Pro-2) Surfactant (Su-1) ... J, O05 alkali-soluble matting agent (average particle size 2μ) ...0.10 cyan dye (
, AIG-1) ・0.005 magenta dye (A
IM-1) ・0.01 Swelling agent (WAX-1)
・0.04 gelatin...
0.8 In addition to the above composition, each layer also contains a coating aid of 5u-
2. Dispersion aid 5u-3, hardener H-1 and H-2, preservative DI-1, stabilizer 5tab-1, antifoggant AF-
1° AF-2 was added.

El-1 Average grain size 0.487Lm, average silver iodide content 7.5%
Monodisperse surface low silver iodide content emulsion E layer-2 Average grain size 0.32ILm, average silver iodide content 2.0%
Monodisperse, uniform composition emulsion E+a-3 Average grain size 0.78 l, average silver iodide content 6.0% Monodisperse surface low silver iodide content emulsion m-4 Average grain size 0. 95#Lm, average silver iodide content 8.0%
Monodisperse surface-low silver iodide-containing emulsions E+a-1, Em-3 and Em-4 are disclosed in JP-A-60-13
It is a silver iodobromide emulsion mainly composed of octahedrons and has a multilayer structure adjusted with reference to publications No. 8538 and No. 61-245151.

Moreover, in all of Em-1 to Em-4, the average value of particle size/particle thickness was 1.0, and the width of particle distribution was 14%, 10%, and 12%, respectively.

S” CfHs C, I+.

n■ M-2 Q Q Q C-t M-1 Q H O■ 0■ c, n5Q) UV-2 ((CHI・CH302C)Iri, CCII, SQ, (
C) I, ), ) J (CHI) tsOJ u-1 ■ II u-2 ! l Na0sS CC00Cell+y C1,-COOC,11,? u-3 c-1 0■ H IC-1 IM-1 tab-I nI+ AP-I AF-2l-1 0i+-30i1-4 The sample thus prepared was exposed to wedge light using white light. , the following development treatment was performed.

Experimental processing> Processing process Processing time Processing temperature Color development (1 tank) 3 minutes 15 seconds 38°C bleaching (l
38°C fixation (1 tank) 1 minute 45 seconds 38°C stabilization (3 tank cascade) 1 minute 38°C drying (
(40°C to 80°C) for 45 seconds The composition of the processing solution used is as follows.

[Color developing solution Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite 4g Sodium bromide
1.3g potassium iodide
l・2+wg hydroxylamine sulfate
2.5g Sodium chloride 0
．． 6g4-amino-3-methyl-N-ethyl-N-(β
-Hydroxylethyl)aniline sulfate 4.8g Potassium hydroxide 1.2g Add water to make 1M, and use potassium hydroxide or 50% sulfuric acid to prepare P)I I
Adjust to Q, 0B.

[Bleach solution] Organic acid ferric complex salt Listed in Table 1 Ethylenediamine disodium acetate 10g Ammonium bromide 150g Glacial acetic acid
10+J1 Color developer
200m ammonium nitrate
Add 30° water to make tX, and adjust to pH 5.8 using aqueous ammonia or glacial acetic acid.

[Fixer] Ammonium thiosulfate 150g Sulfite or sulfite releasing compound listed in Table 1 Disodium ethylenediaminetetraacetate 0.58 Sodium carbonate 10g The above bleaching solution
Add 100 ml of water to make a solution, and adjust the pH to 7.0 using acetic acid and aqueous ammonia.

[Stabilizing solution] Formaldehyde (37% solution) 21 grams 5-chloro-2-methyl-4-isothiazolin-3-one Q, (15 g Emulgen 810 1 serving Add 2 grams of sodium formaldehyde bisulfite adduct and 1
The pH was adjusted to 7.0 using aqueous ammonia and 50% sulfur.

Experiments were conducted by changing the organic acid ferric chain salt and sulfite or sulfite releasing compound in the white liquor and fixer as shown in Table 1 below. However, after the bleaching solution and fixing solution were stored at 38° C. for 5 days, development processing was performed according to the processing steps described above.

The highest density transmitted blue density of the processed film sample was measured using a photodensitometer PDA-85A (manufactured by Ninika Co., Ltd.).

Furthermore, the treated film sample was heated at a relative humidity of 75% and a temperature of 7.
The sample was stored at 0° C. for 10 days, and the transmitted blue density of the same portion was measured in the same manner to determine the rate of decrease in dye density before and after storage.

Furthermore, the amount of residual silver in the highest density area was measured using a fluorescent X-ray method.

In addition, the appearance of the fixer after storage at 38°C for 2 weeks was The results are summarized in Table 1 below.

In the margin table below, HDTA-Fe is ethylenediaminetetraacetic acid 2
Iron ammonium salt, (A-1)・Fe, (A-2)
・Fe.

(A-4)・Fe, (A-7)・Fe, respectively (
A-1), (A-2), (A-4), (A-7) second
means iron ammonium salt.

Furthermore, the O mark in Table 1 means that no abnormality is observed and the condition is good, Δ means that some turbidity is observed, and X means that floating matter or precipitate is clearly observed.
It means that the degree is bad.

As is clear from Table 1 above, the specific organic acid ferric chain salt according to the present invention is used in the bleaching solution, and 0.1% is used in the fixing solution.
When using a sulfite or a sulfite releasing compound in an amount of mol/i or more, the reduction rate of yellow dye was also good, no abnormalities such as precipitation were observed in the fixer, and the desilvering reaction was also completed. It can be seen that it is suitable for rapid processing.

However, it can be seen that even if any of these conditions is lacking, the effects of any of the above examples are lost and the invention cannot be put to practical use.

Example 2 Table 21 was added to the bleaching solution used in Experiment No. 1-4 of Example 1.
1.5 g/gram of the bleaching accelerator shown was added, and the rest was as in Example 1.
An experiment was conducted in the same manner.

The amount of residual silver and unexposed stand cyan stain of the film sample after processing was measured.

The results are summarized in Table 2.

Table 2 (Table 2) Above shows that by using the processing method of the present invention in combination with a specific bleaching accelerator, the suitability for rapid processing is further promoted, and cyan stain is also improved at the same time.

Example 3 A vinyl chloride nozzle with a hole of 0.5 mm in diameter was installed in the bleaching tank and fixing tank of Experiment No. 1-4 in Example 1, and an Iwaki magnet pump Nozzle was applied to the emulsion surface of the photosensitive material.
The experiment was conducted in the same manner except for spraying a treatment solution using -15.

As a result, the cyansteine became 0.03, and the amount of residual silver was significantly reduced.

Example 4 Experiment No. of Example 1: EDT in the fixer used in 1-4
When a similar experiment was carried out by adding 100 g/gram of A-Fe and adjusting the pH to 7.0, the residual silver amount was at a level, and other results were almost the same.

Example 5 Experiment No. 1 of Example 1: 40g/41 of the compounds shown in Table 3 below were added to the fixer and fixer replenisher used in 1-4, respectively.
A similar experiment was conducted.

The results are summarized in Table 3.

Table 3 From Table 3 above, the treatment method of the present invention has the formula [FA]
It can be seen that the desired effects of the present invention are further promoted when the compounds represented by or the compounds of compound group [FB] are used in combination.

Example 6 Experiment No. of Example 1, except that cyan couplers C-2 and C-3 used in 1-6 were replaced with cyan couplers listed in Table 4 with the same mole as C-2 and C-3. When the same processing and evaluation as in Example 1 were performed, almost the same results were obtained.

However, the bleaching fog (cyan fog) was also measured.

The results are shown in Table 4.

As is clear from Table 4, the bleaching fog of cyan was improved by changing the cyan coupler to a cyan coupler preferred for the present invention.

Example 7 A running process was performed using the color negative film and processing solution prepared in Experiment No. 1-4 of Example 1, and the following replenisher.

The composition of the treatment liquid used is as follows.

[Color developer] Potassium carbonate aog sodium bicarbonate 38 potassium sulfite
7g sodium bromide
0.5g hydroxylamine sulfate ip
3.1g4-amino-3-methyl-N-ethyl-N
-(β-hydroxylethyl)aniline sulfate 6.0g Potassium hydroxide 2g Add water to make IIL,
pHIo, 1 using potassium hydroxide or 20% sulfuric acid
Adjust to 2.

[Bleach replenisher] Organic acid ferric complex salt (listed in Table 5) 0.5. 2g ammonium bromide 178g glacial acetic acid
21m ammonium nitrate
Add 35 g of water to make 1 fL, and adjust the pH to 5.8 using aqueous ammonia or glacial acetic acid.

[Fixer replenisher] Ammonium thiosulfate 200g Anhydrous sodium bisulfite 15g Sodium metabisulfite 3g Disodium ethylenediaminetetraacetate 0.88 Sodium carbonate 14g The above bleaching solution
Add 100m Bunsui! ; Set to L and adjust the pH to 8.5.

As the stabilizing replenisher, the stabilizing solution of Example 1 was used.

The processing steps, processing time, processing temperature, and replenishment amount of the running processing were as follows.

(The amount of replenishment is the value per rn' of photosensitive material.) However, the fixing tank was a two-tank countercurrent (45 seconds, two tanks).

The running process will reduce the capacity of the bleach tank by 2 times in 40 days.
This was done until double the amount of bleach replenisher was added. The film sample after the running process was stored in the same manner as in Example 1, and the dye reduction rate and the amount of residual silver in the highest density area before and after storage were measured.

Next, a similar experiment was conducted in place of the organic acid ferric complex salts in the bleach solution and bleach replenisher, and the organic acid iron complex salts shown in Table 5 below.

The results are summarized in Table 5.

Table 5 The descriptions in the table are synonymous with those in Table 1 of Example 1, and (A-
1)・Fe/EDT^・Fe-3/1~1/1 is (A-
1) Fe and E[]TA-Fe were mixed and added at a molar ratio of 3:1 to 1:1 so that the total amount of organic acid iron complex added was 0.25 mol/fL. means.

From the above table, it can be seen that the processing method of the present invention has good dye reduction rate (yellow) and desilvering property.

Patent Applicant Konica Co., Ltd. Representative Patent Attorney Nobuaki Sakaguchi Patent Application No. 63-46919 2 Title of Invention Processing Method for Silver Halide Color Photographic Light-sensitive Materials 3 Relationship to the Person Making Amendment Case Name of Applicant (127) Konica Co., Ltd. 4 Agent Address: 5th Floor, 2nd Building, 7-10-11 Nishi-Shinjuku, Shinjuku-ku, Tokyo (03) 361-0055 (main) FAX: 361-
Contents of the 010:1 amendment (Japanese Patent Application No. 6:1-46919)
1 The following amendments are made to the Meijishu.

1. The scope of claims is amended as follows.

In a method for processing a silver halide color photographic light-sensitive material, which immediately after color development is treated with a bleaching solution and subsequently treated with a processing solution having fixing ability, the bleaching solution is a compound represented by the following bifurcated formula [A]. A method for processing a silver halide color photographic light-sensitive material, characterized in that the processing solution having a fixing ability contains at least 0.1 mol/l of a sulfite or a sulfite-releasing compound.

- Formula [A] [In the formula, AI to A4 may be the same or different,
-C)1. Oll, -C00M or -p03MJt
represents.

M, M+, and L are hydrogen atoms, sodium, and
Represents potassium or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms. ]2 Page 2, No. 1
In the second line, it says ``Natairu.'' Correct it to ``Natairu.''

3. On page 3, line 8, amend the text to read ``a certain defect'' and ``a certain defect.''

4 On page 6, line 7, it says ``Propylenediaminetetraacetic acid ferric chain salt''.
Corrected as "iron chain salt".

5 In lines 14 to 12 from the bottom of page 8, [X has 2 to 2 carbon atoms.
. . . ]" is replaced by "
〜6 substitutions, ゜represents an unsubstituted alkylene group, 〇 is corrected.

6 On page 9, lines 3 to 8, “X has 2 to 5 carbon atoms...
・・・・・・・・・・・・ can be mentioned. "It says "X
represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (eg, propylene, butylene, pentamethylene, etc.). A hydroxyl group is mentioned as a substituent. ” he corrected.

that's all

Claims (1)

[Scope of Claims] In a method for processing a silver halide color photographic light-sensitive material, which immediately after color development is treated with a bleaching solution and subsequently treated with a processing solution having a fixing ability, the bleaching solution has the following general formula [A ] A silver halide color photographic light-sensitive material containing a ferric complex salt of a compound represented by the formula: wherein the processing solution having fixing ability contains at least 0.1 mol/l of a sulfite or a sulfite-releasing compound. processing method. General formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A_1 to A_4 may be the same or different, -CH_2OH, -COOM or -PO_3M_1
Represents M_2. M, M_1, M_2 are hydrogen atoms, sodium,
Represents potassium or ammonium. X represents a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms, and the total number of carbon atoms including branched moieties is 3 or more. ]