JPH04204942A - Processing liquid for silver halide color photographic sensitive material and processing method using processing liquid - Google Patents

Abstract

PURPOSE:To prevent fading of dye and to improve homogeneous dropping of stabilizer by incorporating at least one compd. selected from compds. expressed by formulae. CONSTITUTION:The above processing liquid for silver halide color photographic sensitive material contains at least one compd. selected from compds. expressed by formulae I-V. In these formulae, R1-X1, R2-X2, R3-X3, R4-X4 are SO3M (M is cation), or R1-R4 are aliphatic, aromatic, heterocyclic ring groups, X1-X4 are oxygen, sulfur, formula VI (wherein R5 is hydrogen, aliphatic group, aromatic group, heterocyclic ring group), T1 is -COOR5, aromatic group, heterocyclic ring group, Z1, Z2 are hydrogen or groups which separate by hydrolysis. Thereby, the obtd. processing liquid for silver halide color photographic sensitive material has excellent stability for picture image and causes low environmental pollution.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a processing solution and processing method for silver halide color photographic light-sensitive materials, and more specifically, a silver halide color that is low in pollution and has excellent dye image stability. The present invention relates to a processing liquid for photographic materials and a processing method.

[Background of the invention]

In general, silver halide color photographic materials are subjected to a color development process after exposure for one image, a fixing process following bleaching, or a process that has a fixing ability such as a bleach-fixing process, and then stabilization, washing, and other processing steps. However, in the water washing step that follows treatment with a processing solution that has fixing ability, thiosulfate, which is a compound that reacts with silver halide to form water-soluble complex salts, other water-soluble silver complex salts, and even storage It is known that sulfites, metabisulfites, and the like as constant agents are contained in and adhered to photosensitive materials and are brought into the photographic materials, and if the amount of washing water is small, this will have a negative effect on the storage stability of one image. Therefore, in order to eliminate such drawbacks, the current situation is to use a large amount of running water to wash away the salts from photographic materials. However, in recent years, due to economic reasons such as lack of water resources, rising sewerage charges and utility costs, and pollution concerns, there has been a desire for a treatment process that reduces the amount of washing water and takes measures against pollution.

Conventionally, as a countermeasure against these problems, for example, a method of arranging the washing tank in a multi-stage configuration and causing water to flow countercurrently was proposed in West German Patent No. 2.920, 2.
No. 22 and Niskai Rkai Goldbasser (S, R,
Goldwasser), r water a 71
=1 1 Luit Ken in Immersion Ken Watching of Motion Picture Film (Water
Flow Rate in Immersion
-Washing of Motion-piet
ure Film) J S M P T E, Vo
1, 84, pp. 248-253, May, (1955), etc.

A processing method is also known in which preliminary washing is provided immediately after the fixing bath to reduce the amount of polluting components contained in and attached to the photosensitive material and enter the washing process, and to reduce the amount of washing water.

However, these technologies are not treatment methods that do not use flushing water at all, and therefore water resources have been depleted in recent years.
In addition, this is becoming an increasingly serious problem in a situation where the cost of washing with water is increasing due to factors such as rising crude oil prices.

On the other hand, there is a processing method in which stabilization treatment is performed immediately after photographic processing without washing with water. For example, U.S. Patent No. 3.335,0
Silver stabilization treatment using thiocyanate, which is described in the specification of No. 04, is known. However, this method has the drawback that the stabilizing bath contains a large amount of inorganic salt, so that the surface -L of the photographic light-sensitive material becomes stained after drying.

It has also been found that when this type of stabilization treatment is performed, there is another drawback in that the dye image deteriorates during long-term storage.

On the other hand, when processing color photographic materials such as photographic materials in which the silver halide is silver iodobromide, a stabilizing bath containing formaldehyde is generally used in the final processing step following the water washing bath. There is.

The formaldehyde used in the stabilizing bath has the effect of preventing the physical properties of color photographic materials, especially the occurrence of scratches on the surface of color photographic materials and changes in gradation caused by gradual hardening of photographic materials over time. Furthermore, it is known to be effective against deterioration of the stability of dye images due to unreacted couplers remaining in color photographic materials.

However, formaldehyde, which is added to the stabilizing bath for the purpose of stabilizing dye images, adheres to the photosensitive material and forms adducts with sulfite ions brought in from the prebath (processing liquid that improves fixing ability). Not only does this reduce the dye image stabilizing effect, which is the original objective, but it also has the disadvantage of accelerating sulfurization. To solve these problems, U.S. Patent No. 4,786,5
As shown in the specification of No. 83, it has been proposed to use alkanolamines, but the use of alkanolamines does not tend to have an adverse effect on the yellow stain in the unexposed area, and it can also be said that the sulfurization prevention effect is sufficient. It wasn't.

On the other hand, formaldehyde has been reported in the United States by CIIT (Chemical Institute of Toxicology), which announced that 15pP of formaldehyde caused nasal cavity cancer in rats.
l03H (National Institute for Occupational Safety and Health), ACGIH
(Government Specialist Council for Industrial Hygiene) also considers it to be a possible cause of cancer. Formaldehyde is also subject to strong regulations in Europe, and in West Germany 10 years ago, no formaldehyde was allowed in homes. It is regulated to be below lppm.

Furthermore, in Japan, formaldehyde is classified as a dangerous substance and dangerous drug due to its irritating effect on mucous membranes.
Regulations on organic solvent poisoning under special regulations of the Labor Safety Act, regulations on household goods, regulations on textiles and plywood, and from 1975, new formaldehyde regulations were implemented by the Ministry of Health and Welfare on underwear and baby clothing. There has been a long-awaited technology that can reduce formaldehyde.

Techniques for substantially zeroing or reducing the formaldehyde content in the stabilizing solution include hexahydrotriazine compounds described in JP-A-62-27742 and JP-A-61-151538, as well as U.S. Pat. 4
The tomethylol-based compounds described in No. 859574 are disclosed as means for achieving the above object.

However, although hexahydrotriazine compounds can prevent dye fading under high temperature and high humidity even when formaldehyde is substantially reduced to O, they are not very effective at low temperatures, for example when the relative humidity is 20% or less. There is no,
In addition, the stabilizing solution drips on the back side of the film sample, causing unevenness, which is a problem that can easily occur.Furthermore, although it is not as bad as formaldehyde, there are problems with the storage stability of the stabilizing solution, especially its tendency to sulfurize. It has been found that the storage stability becomes a problem when treated with a low amount of treatment, or even when a low amount of replenishment is used.

In addition, when the above N-methylol compound is used as a formaldehyde substitute, it is not sufficient in terms of preventing dye fading, uneven dripping, and stabilizing solution retention. There is a problem that the liquid storage property deteriorates in one dog. Furthermore, a method using a hexamethylenetetramine compound as a stabilizing solution has been disclosed, but like the hexahydrotriazine compound, this method has the disadvantage that the effect of preventing dye fading under low humidity is weak.

[Purpose of the invention]

Therefore, the objects of the present invention are, firstly, to improve the uneven dripping of the stabilizer solution while preventing fading of the dye even if the formaldehyde content 1 is substantially O; and secondly, to improve the storage stability of the stabilizer solution. Thirdly, the formaldehyde content is reduced to substantially O to improve the safety of the working environment, and fourthly, the washing water is The purpose is to make it possible to save resources and energy without actually using it.

[Means for Solving the Problems] In order to achieve the above object, the present inventors have conducted intensive studies and have arrived at the present invention.

That is, the processing solution for silver halide color photographic light-sensitive materials according to the present invention is characterized by containing at least one compound selected from the compounds represented by the following general formulas CI3 to [v].

General formula [engineering] R, -X, -CII-T.

General formula (n) RI X% General formula Cm) R, -X, -C1-C11-X, -R.

oz, oz.

[In the formula, R1-XI, R2-X2, R3-X3 and R4
-X4 represents S03N (M represents a cation), or RI''R4 represents an aliphatic group, aromatic group, or heterocyclic group, Xl-X4 represents an oxygen atom, a sulfur atom, -s- (R5 represents R1 and R2, R1 and R3, and R3 and R4 may be combined to form a ring, TI represents -COORs, aromatic group, sZl and Z2 representing a heterocyclic group represent a hydrogen atom or a group that is eliminated by hydrolysis.] Furthermore, the method for processing a silver halide color photographic light-sensitive material according to the present invention includes , at least 1 selected from the compounds represented by the above general formulas CI''J to [V]! ! It is characterized by processing with a processing liquid containing.

Further, as a preferred embodiment of the present invention, in the above processing liquid and processing method for silver halide color photographic light-sensitive materials, the processing liquid is a processing liquid or a stabilizing liquid having bleaching ability, and the processing liquid is a stabilizing liquid, and that it is a final treatment liquid;
the processing liquid is substantially free of formaldehyde;
The treatment liquid contains a water-soluble surfactant, and the treatment liquid contains a fungicide.

[Specific structure of the invention]

Preferred processing steps in the processing method using the processing solution of the present invention are as follows: (1) Color development → bleach-fixing → washing → stabilization (2) Color development → bleaching → fixing → washing → stabilization (3) Color development → bleaching + Bleach-fixing → washing with water → stabilization (4) color development → bleach-fixing → fixing → washing with water and stabilizing (5) color development → bleach-fixing → bleach-fixing → washing with water →
Stable (8) Color development → fixing → bleaching and fixing → washing → stable (7
) Color development → bleaching → bleach-fixing → fixing → washing with water → stabilization (8) Black and white development → washing with water → reversal → color development → washing with water → adjustment →
Bleaching → Fixing → Washing → Stabilization (9) Black development → Washing → Reversal → Color development → Washing → Adjustment →
Bleach-fix → Wash → Stable (]0) Color development → Bleach-fix → Stable (11) Color development → Bleach → Fix → Stable (12) Color development → Bleach → Bleach-fix → Stable (] C3 Color development → Bleach-fix → Fix → Stable (14) Color development → Bleach-fix → Bleach-fix → Stable (15) Color development → Fix → Bleach-fix → Stable (18) Color development → Bleach → Bleach-fix → Fix → Stable (17) Black and white development → Washing → Reversal → Color development → Washing → Adjustment → Bleach → Fixing → Stable (18) Black and white development → Washing and reversing → Color development → Washing → Adjustment → Bleach and fix → Stable, but preferably (1), (2), ( 8),
(10).

(11) and (17), more preferably (2).
), (8), (11), and (17), and particularly preferred is step (1).

In the present invention, the processing solution having bleaching ability includes, for example, the bleaching solution or bleach-fixing solution used in the above-mentioned processing steps.

The compounds represented by the general formulas (I) to [■] used in the present invention will be explained below.

In the general formulas [E] to (V), the aliphatic groups represented by R1-R5 include saturated alkyl groups (for example, unsubstituted alkyl groups such as methyl, ethyl, butyl, and benzyl, carboxymethyl, Substituted alkyl groups (hydroxymethyl, methoxyethyl, etc.), unsaturated alkyl groups (e.g. allyl, 2-butenyl, etc.), cyclic alkyl groups (sidelight, cyclopentyl, cyclohexyl, etc.)
etc.

The aromatic group represented by R1-R5 and TI is preferably a substituted or unsubstituted phenyl group, and examples of the substituent include an alkyl group (e.g., methyl, ethyl, methoxyethyl, benzyl, carboxymethyl, sulfopropyl etc.), aryl groups (e.g., eva, phenyl, p-methoxyphenyl, etc.), hydroxy groups, alkoxy groups (e.g., methoxy, ethoxy, methoxyethoxy, etc.), aryloxy groups (e.g., phenoxy, p-carboxyphenyl, etc.), Carboxy group, sulfo group, alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl, etc.), amino group (e.g., N, N-dimethylamino, N-ethylamino, N-phenylamino, etc.)
, acylamide group (e.g., acetamide, benzamide, etc.), carbamoyl group (e.g., carbamoyl, N-
Methylcarbamoyl, N,N-tetramethylenecal/<
-moyl, etc.), sulfonamide groups (e.g., 1, methanesulfonamide, benzenesulfonamide, etc.), sulfamoyl groups (e.g., N-ethylsulfamoyl, N, N
-dimethylsulfamoyl, etc.), alkylsulfonyl groups (e.g., methanesulfonyl, ethanesulfonyl, etc.),
Arylsulfonyl groups (e.g. benzenesulfonyl,
(P-)luenesulfonyl, etc.), acyl groups (eg, acetyl, benzoyl, etc.), and the like.

The heterocyclic group represented by R1-R5 is preferably 5
or 6-membered heterocyclic group, for example, 5-membered ring groups include thienyl group, pyrrolyl group, furyl group, thiazolyl group, imidazolyl group, pyrazolyl group, succinimide group,
Examples of the six-membered ring group include a triazolyl group, a tetrazolyl group, and a pyridyl group, a pyrimidinyl group, a triazinyl group, and a thiadiazinyl group. These heterocyclic groups may further form a condensed ring with a benzene ring, and include, for example, a purinyl group, an imidazolyl group, a benzoxasilyl group, a henzimidazolyl group, a quinolyl group, an indolyl group, a phthalimide group, and the like.

These heterocyclic groups may have an N substituent.

R1 to R5 are preferably aliphatic groups, and XI to x4 are preferably oxygen atoms.

Furthermore, in general formula (II) and [■], R1-Xl
and R2-X2 are preferably the same.

Further - in the formula (rV), R, -X, , R2-x
2 and R3-Xl are preferably all the same,
Further - in formula (V), R+ -X+, R2-
Preferably, X2, R3-Xl and R4-x4 are all the same, and T1 is preferably -COORs.

Examples of the groups Zl and Z2 which are separated by hydrolysis include trialkyl-substituted silyl groups (e.g., trimethylsilyl, etc.), acyl groups (e.g., acetyl, benzoyl, monochloroacetyl, trifluoroacetyl, etc.), sulfonate groups, amino Carbonyl group (e.g. N
, N-dimethylcarbonyl, N-methylcarbonyl, N
-phenylcarbonyl, etc.), sulfonate groups (e.g.
(methanesulfonate, benzenesulfonate, p-toluenesulfonate, etc.).

Zl and Z2 are preferably a hydrogen atom or an acyl group, more preferably a hydrogen atom.

Examples of the cation represented by M include hydrogen ions, alkali metal ions (for example, ions such as lithium, sodium, and potassium), alkaline earth metal ions (for example, ions such as magnesium and calcium), ammonium ions, and organic ammonium ions. Examples include ions (for example, ammonium ions such as triethylammonium, tripropylammonium, and tetramethylammonium), viridicholam ions, and the like.

M is preferably a sodium ion and a potassium ion.

Examples of compounds represented by formulas (I) to (V) are listed below, but the invention is not limited thereto.

[Exemplary compounds]

(+) CIl, 0CIICOOII
(2) CI+30CIlCOOCI+.

0il 0H (3) CI+30CIlCOOC,+15
(4) CIl, 0CIICOO110H0COC
I+3 (5) co3oc++cooct+s
(8) C! 1150cHCOOCtllsI ○coc++3011 (7) CH30CII, C11IOCIICOOC
113(8) CII, 5C1lCOOH)
” OHO1+ (9) CtlsSCIIICOOCHa
(10) (C11,), MClIC0OH(+
3) Cl-130CIIN (C1ls) *
(14) Na○, 5CHCOO1+ (21)
(C)1.0)IcIIcOOcII, (
22) (C1130)2CIICOOC,l1fi
(23) (CtllsO)*ClIC0OC1ls
(24) (CIIts○), ClIC
0OC, II.

(25) (CH30C11, CIl0)tcIlc
OOc113 (28) (CIl33)tcI
IcOOll(27) (CIl33), ClIC0
OC113(28) (C, I, S), ClIC0O
C,H.

(43) (C11,0)ICIIN(C11,),
(44) (C, 1150), CIIN
(C13).

(65) (C, H, O), CIICII (QC,
It5).

(68) (CH,0C112C11,0);C11
C11 (OCII, CIl, OCII,).

(67) (C)1. =CHC11,O), CHCH
(OCII, Cl1=C1+,).

C113CIl3 (74) (C11,)2NCIIN(C1, (75
) (Ctl,), MCIIN (C11,).

0il N(
CIl,).

- Compounds represented by formulas (I) to [V] are easily available as commercial products, but T + -CH0 or 0HGCH
It can also be easily synthesized by reacting O and R+ x+ H-Ra-x4-H at an appropriate molar ratio.

The amount of the compound represented by formulas CI) to (V, 11) to be added is preferably from 0.05 to 20.g, more preferably from 0.1 to 15g, per treatment liquid IQ.

- Compounds represented by formulas [■] to (V) are characterized in that they have better image storage stability, especially under low humidity conditions, than known formaldehyde substitute compounds.

The treatment liquid of the present invention, especially the stabilizing liquid, preferably contains a water-soluble surfactant in order to further enhance the effect of preventing uneven dripping.As the water-soluble surfactant, polyoxyalkylene compounds are preferred. Particularly preferred are compounds represented by the following formula (SI) or (sn) and water-soluble organic siloxane compounds.

General formula (SI) RI X (E I +r-tongue-E 2
U-mi-←E 1 U-'= +”R2 In the formula, R1 represents a hydrogen atom, an aliphatic group, or an acyl group, R2 represents a hydrogen atom, or an aliphatic group. 6E1 represents ethylene oxide, R2
represents propylene oxide, R3 represents ethylene oxide, or an oxygen atom or -R3N- group and R3 is an aliphatic group,
Hydrogen atom or (E1+-TfneeE2bi17(-E3bi,,-R
4, and R4 represents a hydrogen atom or an aliphatic group.

fL+, fo2. +n+, m2. n1. n2 is each 0~
Represents a value of 300.

General formula (s n) A2-0-(B)+o-(C)n-Xr In the formula, A2 is 1
a valent organic group, for example having 6 to 50 carbon atoms, preferably 6 to 50 carbon atoms
35 alkyl groups (for example, 4 such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl)
group) or an alkyl group having 3 to 35 carbon atoms, or an alkyl group having 2 carbon atoms
It is an aryl group substituted with ~35 alkenyl groups.

A preferable group to be N-substituted on the aryl group has 1 carbon number.
-18 alkyl groups (for example, unsubstituted alkyl groups such as methyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl), substituted alkyl groups such as benzyl, phenethyl, or carbon atoms of 2 to 20 alkenyl groups (for example, unsubstituted alkenyl groups such as oleyl, cetyl, allyl groups, substituted aldacol groups such as styryl group). Examples of the aryl group include four groups such as phenyl, biphenyl, and naphthyl, with phenyl being preferred. The aryl group may be substituted at any of the ortho, meta, and para positions, and a plurality of groups can be substituted.

B or C represents ethylene oxide or propylene oxide (however, nl, ml and or 1 are each 0.1
．． 2 or 3).

m and n represent integers from 0 to 100.

xl is a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, examples of which include the groups explained in A2.

Specific examples of compounds represented by formulas (sr) and (S n) will be listed below, but the invention is not limited thereto.

The following margin (compound represented by - formula C3l)) C,,11,5C00+C! +1.0 → -11C, 11
,eCoo-(-C,ll,O→71!C1tll□8
+1-(7C+I1.O→-11e, II+1.Nll
'-(-C,11,O→-1(t-5 C11°C,,11,5-411CIlICI+201111O
−←C11C11,0su---(CIl, C11
,0 one message-;7---11110 +CIICILO
U-5-6-6-(C1l, CILO-)7sugo-1
1□ C11゜+1O--(Cl1CI1.0 U-1,-(: C
11, C1l, OΣ100B-1) (-Compound represented by the formula (SKI), 11) Sl'l-I C
,,11゜-〇美-C,ILOU,11S11-2
C,l+,,-0-(-C,11,0-1l),,
-11SIT-3C, 11, -0-ec, ILO-]
711Sll -4c,,++,,--〇-(-C,1
140-n-11511-14C,,11,,o-fl
-C,1LO-person-115n-15C,It,,-0-
(-C, 11, 0 Utai 11SN-23 St>25 l-28 S■-29 n-31 IT-32 fl-33 n-36 n-37 (River H 1y-39 i1 rl-40 (ill 51 -4.2 5”a -50(n)C, al13i-OCCILC1
l+o), ItSn 51 (n)CI
-11゜0-fClltCIICll, O→-11Sto5" (n) CIall+, Io+c112cll
to→-11rl-65 ll-66 C11°SII -68 5n-72 SIT-76 n-77 rl-78 The amount of water-soluble surfactant added is 0.1 to 4 per stabilizer solution.
It is preferably 0 g, more preferably 0.3 to 20 g.

As a water-soluble organic siloxane compound, the following general formula [
Compounds represented by 5U-I) are preferred.

Each represents a hydrogen atom or a lower alkyl group, and the Rho,
R++ and R12 may be the same or different. Sentences 1 to 3 each represent 0 or an integer of 1 to 30, and P, Q+ and q2 each represent 0 or an integer of 1 to 30. xl and X2 represent UH3L;)l 3 .

Specific examples of the compound represented by the general formula (SU-I) are listed below.

Below margin (water-soluble Yoi a/roxano compound) SLI-1-1, C11゜(CIIJsSi OSi -O5i (C1ls)sneC,l!a (OC+1lr-+T-OtlU-r-2 C11゜(C11, )asi OSi O5i(C1h)aC,
Il, -(-OC211V+rT-011(C11,)
, S+ O (SiO total 5t (CIl+).

C, If, -6-OC, Il, 3yOCl13S U-
r −4 C11°■ (CH3), Si OSi O-5i (C1ls'h■ CJa +0CdldTSi (CHz) sU-I-5 ■ (C113)3SI O3103i (C113).

Hot c311fl-(l-oc211H "OClb5(J-
1-6 C113 (C113:hSi OSi O5i (C1h).

C2114+ 0Ctll=-)rllU-1-7 C11゜(CH3)3Sl O(SiO)D-8i(Ct
b) 3 authors C, +16-(-OC, l+1-U120 5i(C1
la)sUi-8 C1(3 (C1la)asi O(Si-Oh-3i(Cll
s) sC311a(-OCjlrue 5i(CH3)
zU-1-9 (Clla)ssi O(Si Ou-"5i
(Clls)sCa1ls + OC,114-+TT
-si(c!os)sUi-10 (Cll, ), Si -0-3i-0-3i(C113
)3C, +18+OC, 1lr-yh-OC, I+.

SLI-[-11 CIl, C113 U-112 CIl, C1+3 I CIl3-8i OSi (C11-), (OCI
LCtl)toll 1
1 C113CIl, CI+3SU-I
-13 CH3CIl, Cl13CHa 1 1 1 IUi-1
4 Clla Cll3 C1l*
CHsl 1 1
(SLI-1-15 C113C13C1l, CIl.

C113-8i-O-8i-0-3i -0-3i-C
1131] l I C11,CIl, (CtL)3CI+3(QC,1Ld
o et al. 1.1a);0C11゜5U-r-+ 6 C113CI13C11,CI+3 I (11 (0-CIl, C11 go(-0CII t Cll
1→,,QC-IIsSl,J-]-+1 CIl, C1l, CIl,
CIl.

(0-C11, C11→-(scream 1.C11,-Momme-0-
OCI+.

■ U-118 CIl, CIl, C113C113SU
-4-19 C1ls CllI C1+3SUi -
20 C113C113C113C11゜1 1 I l5U-I-21 CIl, C, 113C1In II l 5U-1-22 CH13Cll5 CIl, 1lC113I
1] ]l5U-I
-2 3113C11,C113 ll し1ltc11tL11zlrlargell*L;1ltL
lj L;H! 1 The amount of these water-soluble organosiloxane compounds having polyoxyalkylene groups added is within the range of 0.01 to 20 g per stabilizer, and has good effects, especially in preventing precipitation and reducing yellow stain. Effective in preventing occurrence.

If it is less than 0.01g/1, stains on the surface of the photosensitive material will be noticeable.
If it exceeds 20 g/Jl, a large amount of organic siloxane compounds will adhere to the surface of the photosensitive material, resulting in accelerated staining.

The water-soluble organic siloxane compound of the present invention can be used, for example, in JP-A-47-18333, JP-B-55-51172,
Japanese Patent Publication No. 51-37538, Japanese Patent Application Laid-Open No. 49-82128, and U.S. Patent No. 3,545. ! It means a general water-soluble organic siloxane compound as described in the specification of No. 370 and the like.

These water-soluble organic siloxane compounds are generally available from UCC (Union Carbide Company), Shin-Etsu Chemical Co., Ltd., and the like.

In the present invention, "substantially no formaldehyde is contained in the stabilizing solution" means that the stabilizing solution contains 0/11 and 0.2 g or less.

In the present invention, the preferred amount of replenishment to the stabilizing bath is 800 or less per rn' of the photosensitive material, but excessive reduction in the amount of replenishment may cause discoloration of the dye, precipitation of salts on the surface of the photosensitive material after drying, etc. More preferably 100m sentences or more 820
It is less than m sentences.

Further, the specific setting of the replenishment amount varies depending on the tank configuration of the stabilizing bath, and it is possible to set it to a lower value as the number of tanks increases.

The pH of the stabilizing bath according to the present invention is preferably in the range of 5.5 to 11.0, particularly 7 to 1 to promote the effects of the present invention.
The temperature range is preferably 15°C to 70°C, more preferably 20°C to 55°C. Furthermore, the stabilizing bath treatment time according to the present invention is 12
It is preferably 0 seconds or less, more preferably 3 seconds to 80 seconds, and most preferably 6 seconds to 60 seconds.

In the present invention, when there are two or more stabilizing baths, it is recommended to use a countercurrent method (a method in which the stabilizing bath is supplied to the rear bath and overflows from the front bath) in order to achieve the effects of the present invention, especially in terms of lower pollution and improved image preservation. Particularly preferred.

- In the present invention, the stabilizing liquid preferably contains a chelating agent having a chelate stability constant of 8 or more for iron ions.
il len * A, E, Martell, 5ta
brity Con5tants of Metal
-ion Complexes'', ThaChami
cal 5ociety, London (11184
), S, Chaberek *A, E, Martell
li, “Kano Ganic SequeStering
It means a constant generally known by Agent S''Jiletsu (195B) and others.

Examples of the chelating agent having a chelate stability constant of 8 or more for iron ions include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. Note that the above-mentioned iron ion means ferric ion (Fe2.).

Specific examples of compounds of chelating agents having a chelate stability constant of 8 or more with ferric ions include, but are not limited to, the following compounds: ethylenediamine diorthohydroxyphenylacetic acid, Diaminopropane tetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediamineniprobionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid , glycol ether diamine tetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, l-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2 , 4-)licarponic acid, l-hydroxy-1-phospho7'propane-1,2,3-)licarponic acid, catechol-3,5-diphosphonic acid, sodium birophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate. and particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimedylenephosphonic acid, l-hydroxyethylidene-1
j-diphosphonic acid and the like, among which 1-hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

1] The usage amount of the chelating agent mentioned in 2 is 0.01 per liter of stabilizer.
~50g is preferred, more preferably 0.05~20g
Good results can be obtained within this range.

Further, as a clever compound to be added to the stabilizing solution, an ammonium compound can be mentioned. These are supplied by ammonium salts of various inorganic compounds, including ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphorus, ammonium phosphite, and fluoride. Ammonium chloride, acidic ammonium fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, adipic acid Ammonium, ammonium lauric tricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium digotyl dithiorupamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium phthalate, ammonium hydrogen tartrate l8, ammonium chigi sulfate , ammonium sulfite, ammonium ethylenediaminetetraacetate, ferric ammonium ethylenediaminetetraacetate;
Rum, ammonium lactate, ammonium malate, 71
/Ammonium inate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,4,81-sugar, nitrophenol Ammonium etc. These may be used alone or in combination of two or more.
The amount of ammonium compound added is 0.0 per liter of stabilizer.
The range is preferably from 0.01 mol to 1.0 mol, more preferably from 0.002 to 2.0 000 mol.

It is preferable that the stabilizing liquid contains a metal salt in combination with the chelating agent, and such metal salts include Ba, Ga,
, Ce, Go, In, La, Nn, Ni,
Bi, Pb, Sn.

There are metal salts of Zn, Ti, Zr, Mg, An or Sr, which can be supplied as inorganic salts such as halides, hydroxides, sulfates, carbonates, phosphates, acetates, or water-soluble chelating agents. The amount used is 1 per stabilizer IJI.
The range is preferably from X 10-' to 1xio-+ moles, more preferably from 4X 10-4 to 2X to-2 moles.

Organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH adjusters (phosphates, borates, hydrochloric acid, sulfates, etc.), etc. can be added to the stabilizing solution. .

These compounds may be added in any combination of amounts that are necessary to maintain the pH of the stabilizing bath and do not adversely affect the stability of color photographic images during storage and the generation of precipitates. do not have.

In the present invention, the following formulas [B-1] to [
When the compounds represented by [B-3] are used in combination, the desired effects of the present invention can be better achieved.

General formula [13-1] [In the formula, R1 is an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, an amine group, a carboxylic acid group (including its salt), or a sulfonic acid group (including its salt) ) (2 and R3 each represent a hydrogen atom, a halogen atom, an amino group, a nitro group, a hydroxyl group, an alkoxycarbonyl group, a carboxylic acid group (including its salts), or a sulfonic acid group (including its salts) .M represents a hydrogen atom, an alkali metal or an ammonium group,] General formula B-2] - Formula [B-31s 1?1 [wherein, R4 is a hydrogen atom, a halogen atom, an alkyl group,
Aryl group, halogenated alkyl group, -R12-OR+
3, -CONHR14 (here) i12 represents an alkylene group, R13 and R's each represent a hydrogen atom, an alkyl group, and an arylalkyl group), represents an arylalkyl group, and l (5 and R6 each represent a hydrogen atom) , halogen atom, halogenated alkyl group.

Represents an alkyl group, R7 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a halogenated alkyl group, an arylalkyl group + R15-Q)716, -〇0N)I
Represents Rl 7, where R15 is an alkylene group, RI6
．． RI7 both represent a hydrogen atom and an alkyl group),
R8, R9J (10, R1+ represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an amine group, or a nitro group) Next, regarding the compounds represented by formulas [B-1 to [B-3] explain.

Specific examples of the compound represented by the general formula [B-1] include:
The following exemplified compounds may be mentioned.

CB-1-1) (B-1-2
) (B-1-3) (B-1-4
) (B-1-5) (B-1-8
) (B-1-7) (B-1-8
) (B-1-9) (B-1-1
0) (B, l-11) (B-1
-12) NH.

(B-1-13) (B-1-14
) (B-1-15) (B-1-1
8) (B-t-17) (B-1-+
g) NH2 (B-1 to 19) 8μ The compound represented by the above formula [B-1] is known as a preservative for mandarin oranges and is commercially available, and those skilled in the art can easily understand it. can be obtained.

Among the above exemplary compounds, preferred compounds are [B-1
-11, [R71-21, [B-1-3], [B-
1-4, 1 and [B-1-5].

The compound of general formula [B-1] used in the above invention is:
It is preferably used in an amount of 0.03 to 50 g, more preferably 0.12 to 10 g, and particularly preferably 0.15 to 5 g per 141 of the stabilizer of the present invention.

Specific examples of the compounds represented by formulas [B-2] and [B-3] are described below, but the invention is not limited thereto.

[B-2-1] 2-methyl-4-inthiazoline-3-
[8-2-2]5-chloro-2-methyl-4-thiaralin-3-one [B-2-3]2-methyl-5-phenyl-4-thiazolin-3-one [B -2-4]4-bromo-5-chloro-2-methyl-
4-inchanrin-3-one [B-2-5] 2-) = troxymethyl-zoline-
3-one[B-2-6]2-(2-ethoxyethyl)-4-inchanrin-3-one[B-2-7]2-(N-methyl-carbamoyl)-4
= inthiazolin-3-one [B-2-8]5-bromomethyl-2-(N-dichloropheco-carbamoyl)-4-inthiazolin-3-one [B-2-9]5-chloro-2-(2-phenyl ethyl)-4-inchararin-3-one [B-2-1014-methyl-2-(3.4-dichlorophenyl)-4-inchararin-3-one [B-43-1]1,2-penz Inthiazorin-3-one [B-3-2] 2-(2-bromoethyl)-1,2-benzithiazolin-3-one [B-3-3] 2-methyl-1,2-benzisothiazoline- 3-one [B-3-4] 2-ethyl-5-nitro-1,2-henzinthiaturin-3-one [B-3-5] 2-benzyl-1,2-henzinthiatulin-3-one [B-3-6] 5-Chloro-1,2-benzinthiazolin-3-one These exemplified compounds are listed in U.S. 1.
US Pat. No. 2,767,173, US Pat. No. 2,767,174, US Pat.
No. 870,015, British Patent No. 848,130
Synthesis methods and examples of application to other fields are described in the specification of No. 1, French Patent No. 1,555,418, etc. There are also commercially available products such as Totsubujiito 300 (
Barmakem Asia), Top Sight 600 (Barmakem Asia), Finezite J-700 (Tokyo Fine Chemical U), Proxel GXL (1.C.1
．． l? J)) (7) It is possible to obtain it under the trade name.

These compounds of the formula [B-2), [:13-3] are preferably used in an amount of 0.001=20 g, more preferably 0.00 g per stabilizer of the present invention.
It is in the range of 5-5g.

In the process of the present invention, silver may be recovered from the stabilizing solution17. For example, electrolysis method (Temple Patent No. 2,21119.867
(described in the specification of JP-A-52-73037), precipitation method (described in the specification of JP-A-52-73037, Expanded Patent No. 2,331,220),
The ion exchange method (described in JP-A No. 51-17114, the specification of Expanded Patent No. 2, 548,237) and the metal substitution method (described in the specification of Japanese Patent No. 1,353,805, etc.) can be effectively used. It is particularly preferable to recover silver from the tank solution in-line using an electrolytic method or an anion-exchange resin, as this will improve suitability for rapid processing; however, silver recovery from overflow waste solution, May be recycled and used.

In addition, the stabilizing solution can be subjected to ion exchange treatment, electrodialysis treatment (see JP-A No. 81-28949) and reverse osmosis treatment (see JP-A No. 81-28949).
240153 and Japanese Unexamined Patent Publication No. 240153 and JP-A No. 254151). It is also preferable to use wood that has been deionized in advance for use in the stabilizing solution. That is, the anti-mold properties of the stabilizer, the stability of the stabilizer, and the image storage stability can be improved. Any means of deionization may be used as long as it reduces the concentration of Ca, l+1g ions in the washed water after treatment to 5 ppm or less, but for example, treatment with ion exchange polar fat or reverse osmosis membrane may be used alone or in combination. is preferred. For information on ion exchange resins and reverse osmosis membranes, see Technical Report No. 87-1f184 and Technical Report No. 1119-2051.
It is described in detail in issue 1.

The salt concentration in the stabilizing solution is preferably I000 ppm or less, more preferably 800 ppm or less.

After the stabilization treatment, no water washing treatment is required2.
Rinsing with a small amount of water within a very short period of time, surface cleaning, etc. can be carried out as desired.

Color developing agents used in the color development process include:
Although there are amine phenol compounds and p-phenylene diamine compounds, in the present invention, dophenylene diamine compounds having a water-soluble group are preferred.

Such a water-soluble group has at least one group in the amine group of the p-phenylenediamine compound or the benzene nucleus 1-, and a specific water-soluble group is -(CH2).

-G)+20)1, 4CH2)s-NHSO2-(CH2) ,,rcH.
,,-(CH2)s-0-(CH2)n-CI+3,-
(CH2CHzO)ncJ2m-+ (IID and n are each an integer of 0 or more in Table 1.), -COOH group, -S
Preferred examples include 038 group and the like.

Specific examples of color developing agents preferably used in the present invention are shown below.

Margin below [Reli color developing agent] (8-1) C, It, C, 11, N11SO
,C11゜＼／Nll.

(A -2) c, ++a C, 11,011\
/ N11゜(A-3)C・lli＼10・11・011Nll.

(A")C,l16 C,1LOC113\/N11゜(A"C,ll,C,1LO11\/ Among the color developing agents exemplified above, examples No. 1 and (A~1) are preferred for use in Invention 1. ), (A-2), (A
-3), (A-4), (A-8), (A-7) and (A
-15).

The amount of color developing agent added is 0°5 per 131 color developing solution.
It is preferable that the amount of Xl0-2 mol or more is more than 1. OX10-1 mole, most preferably 1.5X10-2~? , O
It is in the range of Xloi moles.

The above-mentioned color developing agents are usually used in the form of salts such as hydrochloride, sulfate, and P4 luenesulfonate.

The color developing solution used in the color development processing step contains alkaline agents commonly used in developing solutions, such as sodium hydroxide,
Potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, borax, and the like can be included. Furthermore, various additives,
For example, benzyl alcohol, alkali halides such as potassium bromide or potassium chloride, development regulators such as citradinic acid, preservatives such as hydroxylamine, hydroxylamine derivatives (such as diethylhydroxylamine), and hydrazine derivatives (such as hydrazine derivatives). ) or sulfites.

Furthermore, five types of antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained.

The pH of the color developer is usually 7 or higher, preferably about 9.
~13.

The color developing solution contains antioxidants such as tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose or hexose, and pyrogallol-1 as necessary.
, 3-dimethyl ether, etc. may be contained.

In the color developing solution, various chelating agents can be used in combination as metal ion pricking agents.For example, the chelating agents include aminopolycarboxylic acids such as ethyl-1/diaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc. Organic phosphonic acids such as hydroxyethylidene-1,1-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphonic acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane-1,2 , 4-tricarboxylic acid, and polyphosphoric acids such as tripolyphosphoric acid and hexametaphosphoric acid.

The preferred replenishment amount of the color developing solution in continuous processing is as follows:
．． 1.5 sentences or less per 0rn' is preferable, more preferably 250m sentences to 900 sentences, still more preferably 3
00 Otomi ~ 70h sentence. Also, the amount of applied silver i gim'
For the following photosensitive materials: 400 per 1.0 photosensitive material
+m sentences or less is preferable, more preferably 150 m1 or less, still more preferably 100++41 or less, most preferably 50 m sentences or less.

The bleaching agent used in the bleaching solution or bleach-fixing solution in the present invention is a ferric complex of an organic acid represented by the following formula (A) or CB) and exemplified compounds shown in A'-1 to A'-16 below. Examples include ferric complex salts.

General formula (A) [wherein, Al-A4 may be the same or different, -CH20H, -'C00N or -Po3MIN
Represents 2.

M, Ml, M2 each represent a hydrogen atom, an alkali metal or ammonium, X is a substitution having 3 to 6 carbon atoms,
represents an unsubstituted alkylene group] General formula B) In the formula, A1-A4 have the same meanings as defined in the above-mentioned -Momona (A), n represents an integer from 1 to 8, and B1 and B2 may be the same or different, each having 2 carbon atoms
-5 represents a substituted or unsubstituted alkylene group] The compound represented by the general formula (A) will be described in detail below.

A1-A4 may be the same or different, and -C
H20H, -GOON also represents bar P(h)l+82,
X, Ml, M2 each represent a hydrogen atom, an alkali metal (e.g. sodium, potassium) or ammonium,
X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (e.g. propylene, butylene, pentamethylene, etc.),
Examples of the substituent include a water-resistant group and an alkyl group having 1 to 3 carbon atoms.

Preferred specific examples of the compound represented by the above-mentioned -Momona (A) are shown below.

The following margins (A-1') (A-2) (A-3) (A, -4,) (A-5) (A -'6) '' (A -
7) (A=8) (A-9) (A-10) (A-11) (A-12) As the ferric complex salts of these compounds (A-1)-(A-12), these A sodium salt, a potassium salt, or an ammonium salt of the ferric complex IA can be arbitrarily used. From the viewpoint of the desired effect and solubility of the present invention, ammonium salts of these ferric rust salts are preferably used. .

Among the above compound examples, those particularly preferably used in the present invention are (A-1), (A-3), and (A-4).
, (A-5), and (A-9), and particularly preferred is (A-1).

Next, the compound represented by the general formula CB) will be explained in detail.

A]~A4 has the same meaning as above, n represents an integer of 1 to 8, Bl and B2 may be the same or different, and each represents a substituted or unsubstituted alkyl [77 group] having 2 to 5 carbon atoms. (For example, ff ethylene, fluoropylene, butylene.

Pentamethylene, etc.), place! 2! Examples of the group include a hydroxyl group, a lower alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, propyl group), and the like.

Below, the formulas of the compounds represented by the above-mentioned formula CB) are shown below.
Here is an example of a community.

(B-1) (B-2) (B-3) (B-4) (B-5) (E-6,) (B-7) These (B-1) to (B-7) Compound compensation 2M [f
! W' = 2 M t & m sodium salts of these compounds, potassium rum groups or ammonium m) c can be optionally used 6 Among the above compound examples, one is particularly preferably used in the present invention. I, especially (E-1), (B-2), (B-
7,), and the number 19 is (B).
-1).

The amount of organic acid ferric rust salt added is preferably in the range of 0.1 mol to 2.0 mol per μ of the bleaching solution, and more preferably in the range of 0.15 to 1.5 mol/μ. .

In the bleaching solution or bleach-fixing solution, preferable bleaching agents other than the iron rust salt of the compound represented by formula (A) or CB above include ferric complex salts of the following compounds (e.g. ammonium, sodium, potassium, triethanolamine). Examples include, but are not limited to, salts such as

(A'-1) Ethylenediaminetetraacetic acid (A'-2)
) Lance-1,2-cyclohexanediaminetetraacetic acid (A'-3) Dihydroxyethylglycinate (A'
-4) Ethylenediaminetetrakismethylenephosphonic acid [A'-5) Nitrilotrismethylenephosphonic acid (
A'-8) Diethylenetriaminepentakismethylenephosphonic acid (A'-7) Diethylenetriaminepentaacetic acid (A'-
8) Ethylenediaminediorthohydroxyphenylacetic acid (A'-9) Hydroxyethylethylenediaminetriacetic acid [A'-10) Ethylenediaminedipropionate (
A'-11) Ethylenediamine diacetic acid [A'-12
) Hydroxyethyliminodiacetic acid (A'-13)
Nitrilotriacetic acid (A'-14) Nitrilotripropionic acid (A'-1
5)) Liethylenetetraminehexaacetic acid (A”-18
) In the ethylenediaminetetrapropionic acid bleaching solution, 1f of the ferric complex salt of the compound represented by formula [A] or [B] is added to the ferric complex salt of the compound represented by formula [A] or [B].
a or a combination of two or more types can be used.

When two or more organic acid ferric chain salts are used in combination, the above-mentioned -
It is preferable that the ferric complex salt of the compound represented by formula [A) or (B) accounts for 70% or more (in terms of mole), more preferably 80% or more, particularly preferably 90% or more, and most preferably is 85% or more.

The organic acid iron (m) complexes may be used in the form of complex salts, or iron (m) salts such as ferric sulfate, ferric chloride, ferric acetate, ferric ammonium sulfate, ferric phosphate An iron (m) ion complex salt may be formed in a solution using iron, etc. and aminopolycarboxylic acid or its salt, or when used in the form of a complex salt, one type of #I salt may be used. In addition, complex salts of class 29 or higher may be used, and fi! in solution using a ferric salt and an aminopolycarboxylic acid! 1 salt, one type of ferric salt or 21 may be used analogously.
1! may be used analogously.

In both cases, aminopolycarboxylic acid is added to iron (I).
II) It may be used in excess to form an ionic complex salt.

Further, the bleach-fix solution or bleaching solution containing the above-mentioned iron (III) ion complex may contain metal ion complex salts other than iron, such as cobalt, copper, Nilacel, and zinc.

For the bleach solution, S white fixer solution and fixer solution, JP-A-64-29
Imidazole and its derivatives described in the specification No. 5258, or compounds represented by the general formulas (I) to (IX) described in the same specification, and at least one of these exemplified compounds are contained, thereby improving speed. can be played.

In addition to the above-mentioned accelerators, exemplified compounds described on pages 51 to 115 of JP-A No. 82-123459 and pages 22 to 115 of JP-A-83-17445 are also available! Exemplary compounds described on page 25, JP-A No. 53-9!1i830,
Compounds described in Publication No. 53-2.842E1 can also be used in the same manner.

These accelerators may be used alone or 21! The above may be used in combination, and the amount of sardine added is generally about 0.0% per liter of bleaching solution.
The range is preferably O1 to 1008, more preferably 0.
05-50g, particularly preferably 0.05-.15
It is g.

When adding an 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. It can also be added after being dissolved using an organic solvent.

The temperature of the bleaching solution or bleach-fixing solution is preferably 20°C to 50°C, preferably 25°C to 45°C.

The pH of the bleaching solution is preferably 6.0 or less, more preferably 1.0 or more and 5.5 or less. The pH of the bleach-fix solution is preferably 5.0 to 9.0, more preferably 6.0 to 9.0.
It is 0 to 8.5.

The pH of the bleaching solution or bleach-fixing solution is the pH of the processing tank during processing of the silver halide photosensitive material, and can be clearly distinguished from the pH of the so-called replenisher.

A halide such as ammonium bromide, potassium bromide, or sodium bromide is usually added to the bleach or bleach-fix solution. Further, various optical brighteners, antifoaming agents, or surfactants can be contained.

The preferred replenishment amount of the bleaching solution or bleach-fixing solution is 500 mm or less per rn' of silver halide color photographic light-sensitive material, preferably L<2011 mm to 400 mM, and most preferably 40 μM to 400 mm. and
The lower the replenishment amount, the more pronounced the effects of the present invention will be.

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 such as hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate.

As the fixing agent used in the fixing solution or bleach-fixing solution according to the present invention, thiocyanates and thiosulfates are preferably used. The content of thiocyanate is at least 0.1
It is preferably at least mol/ρ, and when processing a color negative film, it is more preferably at least 0.3 mol/ρ, particularly preferably at least 0.5 mol/ρ. In addition, the content of thiosulfate is preferably at least 0.2 mol/liter or more, and when processing color negative films, it is more preferable [2
or more than 0.5 mol/mole.

In addition to these fixing agents, the fixing solution or bleach-fixing solution according to the present invention may further contain m-acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, acetic acid. A pH buffering agent made of various salts such as sodium hydroxide, ammonium hydroxide, etc. may be contained alone or in combination.

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, and compounds known to be added to normal fixing solutions or bleach-fixing solutions such as alkylamines and polyethylene oxides should be added as appropriate. I can do it.

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

The replenishment amount of bleach, bleach-fix solution, and fixing solution is 1rn' for a photosensitive material with a total coated silver amount of 2 g/m'' or more.
Per 5011f: L ~ SOO ■ Cross is usually used, preferably in the range of 100 m to 500 m, and furthermore, the total coated silver i! For photosensitive materials of 4/rn' or less, 20mM to 400mM per photosensitive material In' is usually used, preferably in the range of 30+JL to 100mL.

The pH of the fixer according to the present invention is preferably in the range of 4 to 8.

JP-A-64-295
It is preferable to add the compound represented by the general formula [FA] described on page 56 of the specification of No. 258, and its exemplified compounds. Not only can the effects of the present invention be better exhibited, but also the addition of a small amount of light-sensitive material over a long period of time is possible. Another effect is that very little sludge is generated in the processing liquid having fixing ability during processing.

The compound represented by the general formula [FA] described in the same specification is described in U.S. Patent No. 3,335,1 [11 and U.S. Patent 3,2
It can be synthesized by a general method as described in US Pat. No. 80,718. These compounds represented by formula [FA] may be used alone, and 21! i
The above may be used in combination.

Good results can be obtained when the amount of the compound represented by the formula [FA] ranges from 0.1 g to 200 g per treatment liquid.

The processing time with the bleaching solution and fixing solution according to the present invention is arbitrary, but each is preferably 3 minutes and 30 seconds or less,
More preferably 10 seconds to 2 minutes 20 seconds, particularly preferably 2 minutes
The range is from 0 seconds to 1 minute and 20 seconds.

In addition, the processing time with the bleach-fix solution is preferably 4 minutes or less,
More preferably, it is in the range of 10 seconds to 2 minutes and 20 seconds.

In the processing method of the present invention, it is preferred as an embodiment of the present invention that forced liquid stirring is applied to the bleaching solution, bleach-fixing solution, or fixing solution. The reason for this is not only to better achieve the desired effects of the present invention, but also from the viewpoint of suitability for rapid processing. Forcible liquid stirring here means not the normal diffusion movement of the liquid, but the addition of a stirring means to forcibly stir the liquid.As a forced stirring means, Japanese Patent Application Laid-Open No. 64-222
The means described in No. 258 and JP-A-1-2Of (No. 343) can be adopted.

Furthermore, in the present invention, if the crossover time from the color developer tank to the bleach tank or bleach-fix tank is preferably within 10 seconds, more preferably within 7 seconds, bleaching, which has an effect different from the present invention, can be achieved. Effective against blade burri.

The processing liquid used in the processing method of the present invention has been described above, but the processing liquid may also contain the following additives.

For bleaching solutions, see JP-A No. 2-44347, page (
3) ~Page (0 and bleaching agents described in JP-A-2-43548, pages (37) to (38), P
Usual additives such as H, the amount of acids and nucleic acids to be added, and bleaching accelerators may be used.
Conventional additives such as fixing agents, fixing accelerators, preservatives, chelating agents, etc. described in JP-A-2-43548, page (4) may be used as the bleach-fixing solution. Those described in (37) to (38) may also be used.

The stabilizer according to the present invention may contain bactericidal agents, anti-piping agents, chelating agents, optical brighteners, etc. described in JP-A No. 2-43548, pages (38) to (39). .

In the silver halide color photographic light-sensitive material used in the present invention, the silver halide emulsion is manufactured by Research Disclosure 308119 (hereinafter abbreviated as 1'1D308119).
Those described in can be used. The table below shows the locations.

Item E] [Page of RD308119] Iodine group 4 993 I~A
Section Manufacturing Method Section 993I-A and Section 984E
Crystal habit Normal crystal 9!93I-A twin crystal Xl Epitaxial 〃 Halogen composition -like! 3
Not like item 931-B
9!141-0 Item 11 Replacement
//Metal-containing 994I-D
Term Monodisperse 9951-F Term Solvent Addition,.

Latent image formation position Surface Inside 11951-G section
// Applicable sensitive material Negative 9951-) Item 1 positive (including internal fog particles) // Emulsion mixed and used Item 995I-J Desalination
Item 99511A In the present invention, the silver halide emulsion used is a silver halide emulsion that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are listed in Research Disclosure No. 1784.
3. No. 18716 and No. 308111 (hereinafter abbreviated as 111017643.RD1871G and RD308118, respectively).

The table below shows the locations.

[Item] [RD308119 page] [RI
117B431 (RD1871i1) Chemical sensitizer 1
198 m-A term 23 Ei4B spectral sensitizer 111981V-A-A, B, C23-24 84
8-9D, E, Hlr, 7-term supersensitizer! 16 ff-A-E, Section 7 23-24
848-s mark number 9 inhibitor 998 ■24-25 8
4FJ stabilizer 1198 ■24-25 1341
1. Known photographic additives that can be used in the present invention are also described in the above Research Disclosure. The relevant entries are shown in the table below.

[Item] [RD308119*Page J [RD
I7643]rR[]1B? 16] Color clouding prevention agent 100
Section 2■-1 25 650 Dye image 1001
■-7 Item 25 Stabilizer Brightener 998 V 24 Ultraviolet absorber 1003 ■C,X [UC Item 25-2B Light absorber 1
003 ■ 25-2B light scattering agent 1003 V
II[ Filter Dye 1003 ■
25~28 binder -003IX 2B
651 Static Inhibitor 1006XIIl
27 850 Hardener
1004 X, 26. , 851 plasticizer
3006X[[2711i50 Lubricant +006
XII 27 850 Activator-1005X
l 28-27 E150 Coating aid merting agent +007 It is written in Roja. The relevant entries are shown in the table below.

Item E] [RD308119 page] [R0
17G43] [Rrl18718] Yellow h blur
1001 ■-ri term ■C-G term mapishita six puller 1001 ■-ri term
■CG term diazi coupler 100
1 Vll-D term ■C-G term DIR coupler 1001 ■-F term ■F
Section F AR coupler 1002 - Section F Other useful sections 1001 ■ - Section F Residue release h Blur alkali soluble h puller 1001 ■ - Section E Tree section 4 The additive used in the invention is the dispersion method described in RD108119Xlv. It can be added by etc.

In the present invention, the aforementioned RD1764328 page, RD1
871B, pages 647-8 and RD3081190XIX can be used.

The photosensitive material may be provided with auxiliary layers such as a filter layer and an intermediate layer as described in the above-mentioned RD308119-.

The photosensitive material of the present invention can have various layer structures such as normal layer, reverse layer, and unit structure as described in the above-mentioned RD308119 (1-).

In the present invention, in the photosensitive material, the formula [B-1]
When at least one of the compounds represented by [13-3] is contained, the effects of the present invention can be better achieved.

The present invention is applicable to color paper, color negative film, color reversal film, color reversal vapor, color paper, color film for movies, color film for television, etc. used for general purposes or movies. Although it can be applied to color photographic materials, it is particularly effective in transmission color photographic materials.

〔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 The following stabilizing solution was prepared.

1.2-benzisothiazolin-3-one 0.05
g Deir Side 702 (manufactured by Dear Pawn) 1. O
tQ surfactant CeH + z + 0 (CzHnO) + oHO, 1g additive (
Listed in Table 1) Fixer c wood listed in Table 1)
50 companies Add water and 1! ;L, and the pH was adjusted to 8.0.

After adjustment, the opening area is 10c/9 and 50crn'/u.
After storage at 25° C., the number of days until sulfurization occurred was evaluated. The results are shown in Table 1.

This fixer has the following composition.

Ammonium thiosulfate 200g Ammonium sulfite 20g Urea
1.0g silver bromide
0.2 g of water was added to make a mixture, and the pH was adjusted to 7.0 using ammonium hydroxide or glacial acetic acid.

Below is a blank table. 1 Comparative Compounds I C1, CIl, Ofl As is clear from Table 1, the stabilizing solution containing formaldehyde has extremely poor storage stability, and the stabilizing solutions 1-4 to 1- using comparative compounds In No. 8, the liquid storage property is not necessarily good, especially when the opening area is large. On the other hand, stabilizers 1-9 to 1-1 using the compound of the present invention
It can be seen that the effect of No. 8 is significant when the opening area is large.

Example 2 A stabilizer obtained by removing the fungicide 1,2-benzisothiazolin-3-one and Deiaside 702 from the stabilizer used in Example 1, and further 1,2-benzisothiazolin-3-one and Deiaside 702.
Magnesium 1. When the same evaluation as in Example 1 was conducted using ion exchange water containing 1.5 ppm of calcium and 1.5 ppm of calcium, it was found that when the fungicide was removed, the number of days until sulfurization was 2 to 3.
The schedule has become shorter. From this, it can be seen that a fungicide is necessary for preserving the liquid. Further, stabilizers using other antifungal agents or ion exchange water showed almost the same tendency as the stabilizer containing 1,2-benzisothiazolin-3-one and Deiaside 702.

Example 3 In this example, the amount added in the silver halide photographic light-sensitive material indicates the number of grams per lrn' unless otherwise specified.
In addition, silver halide and colloidal silver are shown 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 1st layer: Antihalation layer Black colloidal silver 0.18 Ultraviolet absorber (UV-resistance) 0.20 Colored coupler (CC-
1) 0.05 colored coupler (CM-2) 0
．． 08 High boiling point solvent (Ofl-1) 0.20 Gelatin 1.5 2nd M: Intermediate layer ultraviolet absorber (UV-1) 0.01 High boiling point solvent (Oil-1) 0.01 Gelatin
1.2 Third Calendar: Low sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (Em-1) 0Jtt (
Em-2) 0.8 Sensitizing dye (S-1) 2.2
X 1O-4 (mol/silver 1 mol)/l (S-2)
2゜5XIO-4(// )tt (S-3
) 0.5X 10″4(/’ ) Cyan coupler (
C'-4) 1.2/l (C'-2)
0.3 colored cyan coupler (CC-1)
0.05DIR compound (D-1)
0.002 High boiling point solvent (Oil-1) 0.5 Gelatin 1.2 4th layer: High sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (Em-3) 2.0 Sensitizing dye (S
-1) 2.2X 1O-4 (mol/silver 1 mol)//
(S-2)2.0XIO-4(// )”
(S-3)0. IX lo-4 (tt) Cyan coupler (C'-1) 0.20//
(C'-2) 0.03"(C'-3)
1.15 colored cyan coupler (CC-1)
0.015DIR compound (D-2)
0.05 High boiling point solvent (Oil-1) 0.5
Gelatin 1.3 5th layer: Intermediate layer gelatin 0.5 6th R = low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (Em-1) 1.1 Sensitizing dye (S
-4) 5XIO-4 (mol/silver 1 mol)tt
(S-5) 2X10=(//) Magenta coupler (M'-1) 0.45 colored magenta coupler (CM-1) 0105DIR compound (D
-3) 0.0+5/l (D-4
) 0.020 high point solvent (Oil-2)
0.5 gelatin 1.0
7th layer: Intermediate layer gelatin 08 High boiling point solvent (Oil-1) 0.2 8th layer: High sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (Em-3) 1.2 Sensitizing dye (S
-8) 1.5X 1O-4 (mol/silver 1 mol)tt
(S-7)2.5XIO-4(// )tt
(S-8)0.7X 1(1'(//) Magenta coupler (M'-2) 0.08//
(M'-3) 0.18 colored magenta coupler (CM-2) 0.05 DIR compound (D-3
) 0.01 high point solvent (Oil-3)
0.5 Gelatin 1.3 9th layer: Yellow filter layer Yellow colloidal silver 0.12 Color stain inhibitor (SC-1) 0.1 High boiling point solvent (Ofl-3)
0.1 gelatin 0.8
10th layer: Low sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (Em-1) 0.30tt
(Em-2) 0.25 sensitizing dye (S-10
) 7x 1o-4 (mol/silver 1 moA) Yellow coupler (Y-1) 0.6tt (Y 2
) 0.2DIR compound (D-2) 0
．． 01 High boiling point solvent (Oi 1-3) 0.15 Gelatin 1.2 11th layer: High sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (Em-4) 0.50//
(Em-1) 0.22 sensitizing dye (S-9)
1.3X 1O-4 (mol/silver 1 mol)// (S
-10) 3X10-4 (tt) Yellow coupler (Y-1) 0.38” (Y-2)
0.12 high boiling point solvent (Oi 1-3)
0.07 gelatin 1.2 12th
Layer: First protective layer fine grain silver iodobromide emulsion 0.40 (average grain size 0
．． 08gm, Agl 2.5EI) UV absorber (U
V-1) 0.10// (UV-2)
0.05 High boiling point solvent (Oil-1) 0.
1tt (Oil 4), 0.1 formalin scavenger (HS-1) 0.5 (M
S-2) 0.2 Gelatin 1.2 13th Calendar: 2nd
Protective layer surfactant (S u -1) 0.005 Alkali-soluble matting agent 0.10 (average particle size 2 h)
) Cyan dye (AIC-1) 0.01 Magenta dye (AIM-1) 0.01 Sheli agent (WAX-1
) 0.04 gelatin
0.7 In addition to the above composition, each layer also contains a coating aid Su.
-2, dispersion aid 5u-3, preservative DI-1, stabilizer 5t
ab-1 and antifoggants AF-1 and AF-2 were added.

Em-1 average particle size 0.46p, rx.

Average silver iodide content 7.0 mol% Monodisperse surface-lowered silver-containing emulsion Em-2 average particle size 0.32 gm.

Average silver iodide content 2.5 mol% Monodisperse emulsion with uniform composition Em-3 average particle size 0.78 pLm.

Average silver iodide content 6.0 mol% Monodisperse surface Low silver oxide containing emulsion Em-4 Average grain size 0.95p (Average silver iodide content 7.5 mol% Monodisperse surface Low Silver oxide-containing emulsions Em-1, Em-35 and Em-4 were published in 1980-13.
It is a silver iodobromide emulsion which has a multilayer structure and mainly consists of octahedrons, prepared with reference to the publications of No. 8538 and No. 61-245151.

In addition, for Em-1 to E11-4, the average value of particle size/particle thickness is 1.0, and the width of particle distribution is 14%, 10%, 12%, and 12%, respectively. there were.

S-5C mountain C,116 Ca Y-2C0 0M-1 Q - UV-1 UV-2 C,116 ■-1-2 ((C1l 2 = (jlso2c112)3CC1
11302 (C1l 2)? ) 2 N (C112)
2sO3K u 1 +1 NaO3S -C-C00CII, (CF, CPI),
11C-COOCIIt(CF, C1', )
, 11u-2 NaO,5-C-COoC,Il,.

CI+, -COOC, II,.

u-3 01(. After applying live exposure using the camera, a running test was conducted under the following conditions.

(The amount of replenishment is the value per door of the photosensitive material.) However, the stabilization process was carried out using a two-tank counter current, in which the final stabilizing liquid tank was replenished and the overflow flowed into the preceding tank. Further, a portion of the overflow from the stabilization tank (275+nj2/tn') was poured into the fixing tank.

The composition of the color developing solution used is as follows.

Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite 3.0g Sodium odor
1.2g potassium iodide
0.6mg hydroxylamine sulfate 25g sodium chloride
0.6g 4-amino-3-methyl-N-ethyl-N-(β-hydroxylethyl) aniline sulfate 4.6g diethylenetriaminepentaacetic acid 3.0g potassium hydroxide 1.2g Add water and prepare II
pH 2 using potassium hydroxide or 20% sulfuric acid.
Adjust to 10 old.

The composition of the color developer replenisher used is as follows.

Potassium carbonate 40g Sodium bicarbonate 3g Potassium sulfite 7g Sodium bromide
0.5g Hydroxylamine sulfate 3.184-amino-3-methyl-N
-Ethyl-N-(β-hydroxylethyl) Aniline sulfate 6.0g Diethylenetriaminepentaacetic acid 30g Potassium hydroxide 2g Add water to make II2,
IIHxol using potassium hydroxide or 20% sulfuric acid
Adjust to z.

The composition of the bleaching solution used is as follows.

1. Ferric ammonium 3-propylenediaminetetraacetate Disodium ethylenediaminetetraacetate 10g ammonium bromide 100g glacial acetic acid
40g ammonium nitrate
Add 40 g of water to make II2, and adjust the pH to 4.4 using aqueous ammonia or glacial acetic acid.

The composition of the bleach replenisher used is as follows.

1.3-Propylenediaminetetraacetic acid ferric ammonium 0.35 mol ethylenediaminetetraacetic acid disodium 2g ammonium bromide 120g ammonium nitrate 50g glacial acetic acid
Add 40 g of water to bring the temperature to 1°C, and adjust the pH to 3.4 using aqueous ammonia or glacial acetic acid.

The compositions of the fixer and fixer replenisher used are as follows.

Ammonium thiosulfate 200g Anhydrous sodium bisulfite 20g Sodium metabisulfite 4.0g Disodium ethylenediaminetetraacetate 1.0g Urea
Add 1.0g water and 1
℃ and adjust the pH to 6.5 using glacial acetic acid and aqueous ammonia.

The stabilizing solution and stable replenisher used in Example 1 were used.

The running process was performed using an automatic developing machine until the stable replenisher was replenished in an amount three times the capacity of the stability tank.

After the running process, the magenta density at the highest density part of the processed film sample was measured, and then the temperature was 70°C and the humidity was 70%R.
Stored for 2 weeks at 70°C, 'tR degree 15
%RH for two weeks, and the maximum magenta density after storage was measured to determine the fading rate of the dye. Furthermore, the state of dirt on the back side of the film sample after the running treatment was observed.

In addition, the liquid from the second stabilizing tank was stored at 25°C in a beaker with an opening area of 50 cm'', and the stability of the liquid (number of days until sulfurization) was evaluated.

The results are summarized in Table 2.

Table 2 In the table, in the evaluation of stains on the back side, ○ means that there is no stain on the back side, × means that there is some staining, and ×
The higher the number, the more severe the degree of contamination.

In the table, in the evaluation of dirt on the inner wall of the stabilization tank, ○ means no dirt at all, △ means slight dirt is observed, × means clear dirt is observed, and the higher the number of X, the more dirt there is. It means that the degree is severe.

As is clear from the results in Table 2, when a large amount of formaldehyde is used, there is no problem with the rate of fading and staining on the back surface, but the storage stability of the solution is significantly inferior, and experiment No.
In the cases of 2-4 to 2-6, although the original fading rate under high temperature and high humidity conditions is satisfactory to some extent, the fading rate of the image is inferior under low humidity conditions. Furthermore, the back surface is stained and the liquid storage stability is insufficient. Moreover, the aldehyde compounds other than formaldehyde in Experiments No. 02-7 and 2-8 were inferior in both the fading rate and the liquid storage stability.

On the other hand, it can be seen that the compound of the present invention is excellent in fading rate, especially in low humidity conditions, and is good in both back surface staining and liquid storage stability.

Example 4 During the run in Example 3, the US Occupational Safety and Health Administration (Occupational Safety and Health Administration)
When the formaldehyde concentration in the air was measured using the formaldehyde quantitative method specified by OSHA, it was 1.2 ppm in Experiment No. 2-3.
The concentration of experiments No. 2-9 to 2-18 was 0. lp
It was below pm. This shows that the use of the compounds of the present invention significantly improves the working environment.

Example 5 In Experiment No. 2-9 of Example 3, the surfactant in the stabilizing solution was changed as shown in Table 3, and the same evaluation as in Example 3 was performed. The replenishment amount of stabilizer is 500n+ per 1 m” of photosensitive material.
I made it 42. The results are shown in Table 3.

Table 3 Comparative Compound 2 Comparative Compound 3. , 11°C11,C00C112CIiC,11,3C11C0
0C11, CllCo11.3SO+Na CJs Comparative Compound 4 C[1+ As is clear from Table 3, Experiment N in the present invention.

It can be seen that by using the surfactants shown in Nos. 3-6 to 3-19, the fading rate, back surface staining, and liquid storage stability were good.

Example 6 Magenta coupler M in the film sample used in Example 3
Same as Example 5 except that the same mole of the magenta coupler listed in Table 4 below was used instead of ``2 and M'-3, and Exemplified Compound 2 was used as the compounds of -119 formulas [I] to [V]. Running processing and evaluation were performed.

The results are summarized in Table 4.

However, the magenta couplers used in Table 4 are those described in Japanese Patent Application No. 1983-32501, pages 208 to 227.

Table 4 R-1 Q R-2 Cl From Table 4 above, it can be seen that the present invention can be achieved by using the pyrazoloazole type magenta coupler represented by the -S formula [M-1] described in Japanese Patent Application No. 63-32501. It can be seen that the intended effects of the invention can be better achieved.

Example 7 Various known sulfite ion-releasing compounds were added to the stabilizing solution of Example 3, Experiment No. 2-13 at a concentration of 0.005 mol/I2, respectively.
The experiment was conducted in the same manner as in Example 1 except that As a result, the fading rate of magenta and the stain on the back side were almost the same, but the shelf life (number of days until sulfurization) of the stabilizer was extended by about 50%.

Example 8 A similar running experiment was carried out except that the following bleach-fix solution was used in place of the bleach solution and fix solution in Example 3, and the rest was the same.

Bleach-fix and bleach-fix replenisher Ammonium thiosulfate 240 g Ferric ammonium diethylenetriaminepentaacetate 150 g Ammonium thiocyanate 30 g Ammonium sulfite 15 g Thiourea
2g2-amino-5-mercapto-1,3,4-thiadiazole
Adjust to 1℃ with 2g water, and adjust pH with acetic acid and aqueous ammonia.
Adjust to 70.

(The amount of replenishment is the value per 1 m' of photosensitive material.) However, the stabilization process was performed using a two-side counter current, and the final stabilization tank was replenished and the overflow flowed into the previous tank. . The experiment was conducted in the same manner as in Example 3, including the film sample.

The results were essentially the same as in Example 3.

Example 9 Instead of the bleaching solution and fixing solution in Example 3, the following bleaching solution and bleach-fixing solution were used, and the stabilization treatment was carried out using a 3-tank countercurrent, which was replenished into the final stabilization tank and added to the previous tank. A running experiment was conducted under the same conditions as in Example 3, except that all the overflow of the bleaching solution was poured into the bleach-fix solution in the subsequent tank.The results were as follows: It was the same as Example 3.

Bleach and Bleach Replenisher Ferric Ammonium Ethylenediaminetetraacetate longl, 3-
Ferric Ammonium Propylene Diamine Tetraacetate 50g Ammonium Bromide 100g Ammonium Nitrate 45g Bleach Accelerator
0.005M ammonia water (27%
) 12mJ2 acetic acid
Add 5 g of water to bring the total volume to 12, and adjust the pH to 6.0 using aqueous ammonia and acetic acid.

Bleach-fix solution and bleach-fix replenisher ferric ammonium ethylenediaminetetraacetate 50g ethylenediaminetetraacetic acid 3g ammonium sulfite 12g ammonium thiosulfate 170g ammonium thiocyanate
70g ammonia water (27%)
The temperature was adjusted to 12 by adding 4.5 m°C water, and the pH was adjusted to 7.2 using aqueous ammonia and acetic acid.

(The amount of replenishment is the value per 1 m'' of light-sensitive material.) Example 10 The following bleach solution, bleach replenisher, fixer and fixer replenisher were prepared.

The composition of the bleaching solution used is as follows.

1.3-Propylenediaminetetraacetic acid Potassium ferric 0.32mol Ethylenediaminetetraacetic acid rJ12 Sodium 10g Potassium bromide 100g Maleic acid
30g sodium nitrate
Add 40g water to make II2,
Adjust pH to 4.4.

The composition of the bleach replenisher used is as follows.

1.3-Propylenediaminetetraacetic acid ferric potassium 035 mol ethylenediaminetetraacetic acid 2.

Sodium 2g Potassium Bromide 120g Sodium Nitrate 50g Maleic Acid
Add 40 g of sodium nitrate solution to 1ε and adjust the pH to 34.

The compositions of the fixer and fixer replenisher used are as follows.

Potassium thiocyanate 120 g Potassium thiosulfate 200 g Anhydrous sodium bisulfite I. Lium 20 g Sodium metabisulfite 4.0 g Disodium ethylenediaminetetraacetate 1.0 g Add water to bring the temperature to 1° C. and adjust the pH to 6.5.

The stabilizer and stable replenisher used were the actual MNo. of Example 3,
2-1 to 2 to 15, and when the same evaluation as in Example 3 was performed, the same effect as in Example 3 was obtained, and in a good environment without odor of ammonia or acetic acid. there were. Furthermore, in addition to the effects of the present invention, by making ammonia and acetic acid free, the bleaching blade burr (B-G-R transmission density) is as low as O, Of ~ 0.03 (and the desilvering property is also good). there were.

Example 11 The following compounds (BAG-1 to
3) 0 per rn” of silver halide color photographic light-sensitive material
．． When 0.015 g was added and the same evaluation as in Example 3 was performed, it was effective in desilvering property and fading rate, and the same results as in Example 3 were obtained for other properties.

BAG-1 Agsc, H4cOOH BAG-2 BAG-3 [Effects of the Invention] According to the present invention, firstly, even if the formaldehyde content is substantially O, the stabilizing solution can be prevented from fading while preventing the stabilizing solution from dripping. Second, the stabilizing solution has good storage stability and is particularly free from sulfidation (sulfidation), and third, the formaldehyde content can be substantially reduced to O2.
As a result, the safety of the working environment can be improved, and the fourth
It is possible to provide a method for processing a silver halide color photographic material, which enables resource and energy saving without substantially using washing water.

Claims (1)

[Scope of Claims] (1) A processing liquid for silver halide color photographic materials, which contains at least one compound selected from the following general formulas [I] to [V]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [V] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1-X_1, R_2-X_2, R_3-X
_3 and R_4-X_4 represent SO_3M (M represents a cation), or R_1 to R_4 represent an aliphatic group, aromatic group, or heterocyclic group, and X_1 to X_4 are oxygen atoms,
There are sulfur atoms, ▲mathematical formulas, chemical formulas, tables, etc.▼(R_5
represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group). R_1 and R_2, R_1 and R_3 and R_3 and R
_4 may be bonded to form a ring. T_1 is -COO
R_5 represents an aromatic group or a heterocyclic group. Z_1 and Z_2
represents a hydrogen atom or a group that is eliminated by hydrolysis. (2) The processing liquid for silver halide color photographic light-sensitive materials according to claim 1, wherein the processing liquid for silver halide color photographic light-sensitive materials is a processing liquid or a stabilizing liquid having bleaching ability. (3) The processing liquid for silver halide color photographic light-sensitive materials according to claim 2, wherein the processing liquid for silver halide color photographic light-sensitive materials is a stabilizing liquid and a final processing liquid. (4) The processing liquid for silver halide color photographic light-sensitive materials according to claim 1, 2 or 3, characterized in that the processing liquid for silver halide color photographic light-sensitive materials does not substantially contain formaldehyde. (5) Claims 1 and 2, characterized in that the processing liquid for silver halide color photographic light-sensitive materials contains a water-soluble surfactant.
, 3 or 4, the processing liquid for silver halide color photographic light-sensitive materials. (8) The processing liquid for silver halide color photographic light-sensitive materials according to claim 1, 2, 3, 4 or 5, characterized in that the processing liquid for silver halide color photographic light-sensitive materials contains an antifungal agent. (7) A silver halide color photographic light-sensitive material is treated with a processing solution containing at least one compound selected from the compounds represented by formulas [I] to [V] according to claim 1. Processing method for silver chemical color photographic materials. (8) The method for processing a silver halide color photographic material according to claim 7, wherein the processing liquid is a processing liquid or a stabilizing liquid having bleaching ability. (9) The method for processing a silver halide color photographic material according to claim 8, wherein the processing liquid is a stabilizing liquid and a final processing liquid. (10) The method for processing a silver halide color photographic material according to claim 7, 8 or 9, wherein the processing liquid does not substantially contain formaldehyde. (11) The method for processing silver halide color photographic materials according to claim 7, 8, 9 or 10, wherein the processing liquid contains a water-soluble surfactant. (12) The method for processing a silver halide color photographic material according to claim 7, 8, 9, 10 or 11, wherein the processing liquid contains an anti-mold agent.