JPS61250647A - Treatment of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To ensure a superior bleach-fixing process for a color photosensitive material contg. silver iodide high in sensitivity by processing the photosensitive material with a processing soln. contg. a peroxide as a bleaching agent. CONSTITUTION:The photographic constituent layers formed on a support comprises an antihalation layer contg. black colloidal silver, and a blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers, and the one of these silver halide emulsion layers nearest to the antihalation layer contains silver halide grains contg. silver iodide and a thickness of the total photographic constituent layers is <=25mum. Such a silver halide color photographic sensitive material is imagewise exposed and developed, and processed with a processing soln. contg. a peroxide as the bleaching agent and capable of bleaching silver. The processing bath having bleaching action or a bath preceding to said bath contains at least one of compds. represented by general formulae [I]-[VI].

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to the processing of silver halide color photographic light-sensitive materials (hereinafter referred to as color light-sensitive materials), and more specifically, the present invention relates to the processing of silver halide color photographic materials (hereinafter referred to as color light-sensitive materials), and more specifically, the present invention relates to processing of silver halide color photographic light-sensitive materials (hereinafter referred to as color light-sensitive materials), and more specifically, the present invention relates to the processing of silver halide color photographic light-sensitive materials (hereinafter referred to as color light-sensitive materials), and more specifically, the present invention relates to the processing of silver halide color photographic light-sensitive materials (hereinafter referred to as color light-sensitive materials). The present invention relates to a processing method of processing with a processing solution containing a peroxide after processing with a color developing solution.

[Prior art]

Conventionally, the following methods have been generally used to process color photosensitive materials. After the color photosensitive material is subjected to imagewise exposure, it is treated with a color developing solution containing an aromatic primary amine developing agent, whereby the silver halide is reduced to metallic silver, and the aromatic primary amine is It is oxidized and undergoes a coupling reaction with a coupler to produce a dye image.

The metallic silver is oxidized to soluble silver halide by a bleaching agent (oxidizing agent) in a bleaching process. Thereafter, by treatment with a fixing solution (for example, a solution containing periosulfate or thiocyanate), the silver complex ions are converted into silver complex ions and removed from the photographic material, leaving only a color image. In actual development processing, in addition to the above-mentioned color development process and the basic processes of bleaching and fixing, there are auxiliary processes for physical photographic image preservation and quality preservation. There is also a method of processing with a bleach-fix solution that is carried out in one bath.

As the bleaching agent used in the bleaching process, red blood salt, #42 iron chloride or 7 minoboricarboxylic acid-metal complex salt, and peroxide are generally used.

Both red blood salt and ferric chloride have strong bleaching blades, and the bleaching speed (
It is a good bleaching agent because it has a fast conversion rate (II conversion rate).

However, since bleaching solutions using red blood salt liberate cyan ions through photolysis and cause environmental pollution, it is necessary to make the treated waste liquid harmless. Also, chloride chloride
Bleaching solutions that use iron have a very low pH and extremely high oxidizing power, so the processing machine equipment that contains them is likely to corrode, and the water washing process after bleaching can cause iron to form in the emulsion layer. It has the disadvantage that it precipitates and causes so-called stain. For this reason, a cleaning step using an organic chelating agent is required after the bleaching treatment, which is not suitable for the purpose of rapid processing and labor saving, and is also undesirable as there is a risk of generating chlorine gas in terms of environmental pollution.

It has been proposed to use an aminopolycarboxylic acid-metal complex salt as a bleaching agent that causes less environmental pollution than the red blood salt and ferric chloride. However, the bleaching solution of the 7-mi/polycarboxylic acid-associated complex salt has low oxidizing power and has an insufficient bleaching edge. For example, when bleaching a low-sensitivity color light-sensitive material that is mainly composed of silver chlorobromide emulsion, the purpose can be achieved, but if the material is mainly composed of silver chloride iodide or silver iodobromide and the color When processing sensitized high-sensitivity color light-sensitive materials, especially color light-sensitive materials using high-silver emulsions, the bleaching effect may be insufficient, resulting in poor desilvering, or oxidation products of color developing agents and couplers may be mixed. The dye produced by the oxidative coupling remains in the state of the reaction intermediate Roif dye even after bleaching, and the dye is not completely formed, resulting in so-called poor color recovery.

In any case, bleaching agents (oxidizing agents) such as red blood salt, #2 iron chloride salt, or aminopolycarboxylic acid metal complex salt have problems such as environmental pollution due to the pollution load of the waste liquid, so the treated waste liquid must be completely rendered harmless. It is preferable to use peroxide methods that do not use metal ions, specifically persulfate ions and/or hydrogen peroxide or compounds that release hydrogen peroxide. Peroxide used as a bleaching agent decomposes into water and oxygen or sulfate, so it does not increase biological oxygen demand (BOD) or chemical oxygen demand (COD), making it advantageous in terms of pollution control. However, for example, persulfate ions are
It has stronger oxidizing power than metal complex salts of iron and organic acids, and has a high redox potential, but silver has a weak bleaching blade and takes a long time to bleach. For this purpose, it is known to use various bleach accelerators in combination, and these bleach accelerators are added to a solution containing persulfate ions or to a prebath prior to a bleach bath, for example, in US Pat. No. 3,707'. , No. 374, 3,7
No. 22,020, No. 3.893,858, Special Publication No. 1973
-28227, JP-A No. 53-94927, JP-A No. 53-
No. 95631, No. 55-25084, No. 55-265
No. 06, Research Disk 4th A--(Research
hD 1sclosure) No. 15704 (May 1977) using a bleaching accelerator such as a mercapto compound or diothyl carbamate compound, or JP-A-55-149944, JP-A-58-8352, JP-A-58- No. 95347, a method has been proposed in which a compound described in No. 95347 is incorporated into a sensitive material, and this technology improves the bleaching edge and speeds up the bleaching time.6 However, even when these accelerators are used, , in a processing solution with bleaching ability that uses peroxide as a bleaching agent,
In a high-sensitivity photographic material that has a black colloidal vibration prevention layer and a silver halide layer containing 3 mol% or more of silver iodide in the closest layer, the film thickness is It has been found that if the particle size is too large, desilvering failure will occur rapidly when continuous processing is performed.

Therefore, in a silver halide emulsion containing silver iodide as described above,
Furthermore, there is a strong desire for the development of a processing solution that can rapidly bleach and fix color light-sensitive materials having a halide prevention layer made of black colloidal silver.

[Purpose of the invention]

Therefore, an object of the present invention is to provide an excellent bleach-fixing method for high-sensitivity silver iodide-containing color light-sensitive materials in the processing of color light-sensitive materials.

A second object is to provide a method for processing color photosensitive materials that has a low risk of environmental pollution and meets the requirements for pollution prevention.

[Structure of the invention]

As a result of extensive research, the present inventor has found that the present inventor has a photographic constituent layer on a support that includes a halide prevention layer containing black colloidal silver and a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer. The layer closest to the antihalation layer among the silver emulsion layers contains silver halide grains containing silver iodide,
The color light-sensitive material in which the total thickness of the photographic constituent layers is 25 μm or less is developed after imagewise exposure, and processed with a processing solution having a silver bleaching ability containing peroxide as a bleaching agent. I found that the purpose was achieved.

The term "photographic constituent layer" as used herein refers to all the layers that are present on the same side of the support as the antihalation layer containing the black colloid fi of the present invention and the silver halide emulsion layer of at least 63/I and that participate in image formation. The hydrophilic colloid layer includes, in addition to the haleysilane prevention layer and silver halide emulsion layer, for example, a subbing layer, an intermediate layer (a simple intermediate layer, a single filter layer, an ultraviolet absorbing layer, etc.), a protective layer, etc.

Most preferred implementation of the invention! ! The above general formula (1) ~
The present inventor has found that the object of the present invention can be achieved more effectively by containing at least one of the compounds represented by [■].

General formula [1] General formula (II) General formula (1) General formula CIVI General formula (V) General formula (VI
) In the general formula (1), Q is a heterocycle containing one or more N atoms (
X' B represents a fullylene group having 1 to 6 carbon atoms, M represents a divalent metal atom, and X and X' are =S, =O or =N
R'', and R' represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (at least one 5 to 6 truly unsaturated ring is fused thereto); R3 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (at least one unsaturated ring of 5 to 6 shells is attached to this) (including condensed ones) or amide 7
R2t R3fR4-Rs* R and R' each represent a hydrogen atom, a furkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, a 7-mino group, an acyl group having 1 to 3 carbon atoms, an aryl group, or represents an alkenyl group, provided that R1
and R3 may represent -B-8Z, and R and R',
R2 and R1, R1 and R5 may each be cyclized with each other to form a heterocyclic residue (including one in which at least one unsaturated ring of 5 to 6 shells is fused thereto).

Ra, R? represents each, R1 is an alkyl group or -(CHz)ngsO
, represents e, where Rs is -(CH2) n s SO
3”, み represents 0 or 1, )GO is an anion,
髫、 through 口 and nl through n each represent an integer of 1 to 6, +15 represents an integer of 0 to 6, R6 is a hydrogen atom,
Alkaline. However, Q' has the same meaning as Q above. D represents a simple bond, a fullylene group or a vinylene group having 1 to 8 monomers, and q represents an integer of 1 to 10. multiple D
may be the same or different, and the ring formed with the sulfur atom may be further fused with 5 to 6 unsaturated rings,
The compounds represented by the above general formula include di-/- and salts thereof.

That is, the present inventor continuously produced a high-sensitivity fine-grain color light-sensitive material having black colloidal silver as an antihalation layer and a silver halide emulsion layer (three layers in total) containing a silver iodide-containing emulsion in an adjacent layer. Focusing on the phenomenon that the desilvering performance of silver iodide deteriorates noticeably when the silver is treated, we have conducted intensive research and found that when treated with a processing solution containing peroxide and having bleaching ability, the silver iodide to be treated It has been discovered that when the thickness of the photographic constituent layers of the color light-sensitive material contained therein is reduced below a certain value, the bleach-fixing properties are significantly improved and desilvering defects are improved.

Furthermore, this phenomenon occurs when the thickness of the photographic constituent layer of the silver iodide-containing color light-sensitive material increases.
It has been discovered that the desilvering defects occur at the boundary between the silver iodide-containing silver halide emulsion layer and the silver iodide-containing silver halide emulsion layer.

Furthermore, the present inventor has discovered that when a specific bleaching accelerator is added to a bleach-fixing solution using peroxide as a bleaching agent, the film thickness of the photographic constituent layers including the colloidal silver-containing antihalation layer and the silver halide emulsion layer is increased by gelatin. If the film thickness) exceeds a certain value, a good bleaching accelerating effect cannot be obtained, but if the thickness of the photographic constituent layer (gelatin film thickness) of the color photosensitive material is below a certain value, bleaching will be accelerated by the specific bleaching accelerator. We have discovered the surprising fact that the effects are significantly enhanced.

According to a preferred embodiment of the present invention, the thickness of the photographic constituent layer of the color photographic light-sensitive material is 22 μm or less, more preferably 20 μl or less, particularly 18 μm or less. It has been found that the object of the present invention can be achieved more effectively by this.

Furthermore, in the most effective embodiment, the above-mentioned object of the present invention can be most effectively achieved by a processing method in which a fixing process is performed after the color development process and as a preprocessing step of the bleach-fixing process. I found it. Hereinafter, this fixing process will be referred to as a pre-fixing process or pre-fixing, and the processing liquid used in the pre-fixing process will be referred to as a pre-fixing process liquid or pre-fixer, or a pre-fixing process liquid or a pre-fixing bath.

The bleach accelerator of the present invention has the general formula (1) or Vl
'), typical examples include, but are not limited to, the following:

[Exemplary compounds]

(1-3) (I-4) (1-5>
(1-6) Ui2UuUII
co2ctt, c
o2coon (f-7)
(1-8) (r-9) (
1-10) ([-111(1-12) (I -13) (1
-14) CH2CH2C00H (+ -23) (1-24) (r -2
5) (1-26) (1-27)
(r -28) (1-35)
(1-36>■ (I-37) (118)
(II-1) (II-2>
SS S5 (■-3)
(U-4) (II-5)
(II-6>(II-7)
(II-8>”9) (II-10)
(■-River (If -12) (II-13) (II -14)
(II-15) (If-16)
(II-17) (I[-18)
(II-19) (It-20> S (ll-21) (If-22) (II-23) (■-24) (II-25) (II-26) (II-27) (II-28 ) 112N-C5NHNHCS-Ni12(II-29) (II-30) (n-31> (■-32) (II-33) (II-34) H2N-CSNH(CH2)2NHCS N13(I
I-35) H2N-CSNH(CH2)4NHCS N13(I
I-36> 82N-CSNH(CH2)sNHCS-N13(II
-37) S (n-38) (II-39) (II-40) (If-41) (II-42) (n-43) (■-44) (II-45) (II-46) ( ■-47) (n-48) (II-49) (U-50) ' (n -51) (II-52) (n -53) (II-54) (II-55) (II-56) (■-57) (If-58) (II-59) (II-60) (It-61) (II-62) (n-63) (II-64> (n-651 (n-66) II-67) II Na Na (II-68>(11-69> (II-70) (n-71) (It -72) (n-731 (■ -74) (II-75) CHiNHCH2CH2NHCSCH2CHtCH2C
OOH (If-76) (■ -77) (U-78) (fl-821 (IT-83) (If-84) (n-85) (■-86) (II -87) (If-88) (II-89) (II-90> (■-■) (U-92) (II-93) (II-94) (■-95) (n-96) ■ (II-97) S (n- 98) (II-99) (It-100) (II-101) (n-102) (n-103) (■ -104) (II-105) (It-106) (If-107) (II- 108) (II-110) (II-111> (II-
112) (n -113) (I
I-1141 (II-1151 (If-116) (II-117) (If-
118) (II-119> (
n -120) (If -121)
(II-122)S (II-1231(ll-124) (It-125) (
ff -126) (II -1271 (If -128
>(II-129)
(II-130)Nl-131)
(fl -132) (II -1331(n
-134) rH5 (II -135) (
If -136) (n -137)
(U-138) (n-139)
([1-140) (I[-141)
(II-142)(
II-143) (n-144) H (II-145) (It -146) H (n-147) H (II-148) (II-149) (II-150) (If-151) (tl- 152) (II-154) (n-155) (■-156) (n -157) (■-158) H2N-C112CH2-5H (II-2> (III-3) (Ill -4) (III- 5> HOOC-C)12CH2・5)I (III-6> (III-8) (1-9)C
Hyo(II[-to) (III-11) (III-12) /-1\ ON-CH2CH2-5H (I[l-'13) CH3 (DI -14) CH2CH2-SH (1-151(III -16) (III-17) (III
-18) CH2 H3 (I[I -19) (1-2
0) (III-21) (I
[[-22)CH2CH2-SFI (III-23) (I[-
24) ([-251(III-26) (III-27) H (I[[-28) (I[l-29) (II
I-30) (I[[-31)
(III-32>(I[1-33> (III-34) (I[l-36) (I[[-37) (IV-1) CHyoCH3 (IV-2) CH.

■ CI(3 (■-3) (IV-4) (IV-5> CI3 CH3 (V-1) (V-2) (V
-3) ' (V-4)N -
N N -N (V-
5) (V-6) (V-7)
(V-8) (V-9)
(V-10) (V-11)
(V-12>un
gH(V −131(V −1
4) un (V -15) (V -1
6) (V -17) (V
-18) (V -19) (
V-20) bH5H (V-21) (V-22
) (V -23) (V -2
4) (V-25), (V-2
6) (V-27) (v-zs)
(V-29) (V-3
0) (V-31) (V-32
>(V-33) (V-34)
(V-35) (V-36
) (V-37> (V-38
)(V-39) (V-40) (V-41) (V-42) (V-43) (V-4
4) (V -45) (V
-46) (V -47)
(V-48) (V-49)
(V-50) (V-51)
(V-52) (V-53)
(V-54)H3 (V-55) (V-
56>(V-57) (
V-58) (V-59)
(V-60) (V-61)
(V-62) (V-63)
(V-64) (V-65)
(v-66>(V-671(V-68) (V-69) (V-70>
(V-71) (V-72)
(V -73> (V -7
41 (V-75) (V-7
6) (V-77) (V-7
8) (V -79) (V
-80) (V -81)
(V-82)N13
Llla (V-83) (V
-84) (V-85) (V
-86) (V-87) (V
-88) (V -89)
(V-90) (V-91)
(V-92) (V-93>
(V-94) (CH2)4NH2N13 (V -95) (V-9
6) (V -97) (V
-98) CH2NH2CH2Cl2NH2 (V-99> (V-10
0)(C11□)38H2(CFI2)aNH2(V
-101) (V -10
2) 2H5 (V −103) (V −
104) (V-105)
(V -106) (V -107) H2 (V -108) (V -109) (V -tto) (V -111) (V -112) (V -113) (V -114) (V -115 ) (V -116) (V -117) (V -118) (V -119) SR5H (y-120) (V -121) (V -122) (V-123)' (V-124
>(V-125) (V-1
26) (V -127> (V
-128) (V -129)
(V-130>(V-131)
(V -132) (V -133>
(V-134)Nl2
SH(V-135)
(V -138) SO Yo Na (V -137) (V-138
>(V-139) (V-1
40) (V-141) (V-1
42) (V 143) (V-1
44) (V −145) (V −
146) (V -147) (V
−148>(V −149>(V
-150) (V -151) (
V-152) (V-153)
(V −154) (V j 155)
(V -156)I (V -157> (y 15B
)(V −159) (y + 1
60) (V -181) (V -
162) (V -163) (V
-164) (V -165) (V
-166) (V -167) (V
-168) (V -189)
(V-170>(V-171>
(V-1727)Jl-SH (V-173) Kozue (V-174) (V
-175) SH5H (V -176) SH (V -177) (V -17
8) (V -179) SH (V -180) (V -18
1) (V -182) (V -
183) bit
5H (V -184) N=N I SH (Vl-1) (Vl-2) (
Vl -3) (Vl -4)
(Vl -5) (Vl-6> (W-
7) (Vl-8) (W-9)
(W-10) (Vl-11>
(Vl-12) (Vl-13) (V
l-14> (Vl-15) (
■-16) (VI-17> (■-181
(W-19) (■-20) (Vl-21
) (VI-22) (Vl-23)
(W-241(Vl-25>(Vl-26)
(Vl-27) (Vl-2
8) (VI-29) (W-30)
(W-31) (Vl-32)
(V[-33) (Vl-34)n■ (Vl-35> (Vl-3
6) The above compounds are described, for example, in British Patent No. 1,138,84.
No. 2, JP-A-52-20832, JP-A No. 53-28426
No. 53-95630, No. 53-104232,
It can be easily synthesized by known techniques described in US Pat. No. 53-141623, US Pat. No. 55-17123, US Pat.

The bleaching accelerator of the present invention only needs to be present when bleaching the silver image obtained by development, and is preferably added to a processing bath having bleaching ability, and is preferably added to a processing bath having bleaching ability. It is also preferable to add the compound to the pretreatment solution and bring it into the bleach-fixing bath by bringing it into the color photosensitive material. Alternatively, a method may be used in which the compound is incorporated into the color photosensitive material in advance during the 91 manufacturing process, and dissolved and incorporated into the bleach-fixing bath.

These bleach accelerators of the present invention may be used alone or in combination.
When the bleaching accelerator is added to a processing solution having bleaching ability or a bath (pretreatment solution) preceding those baths, the amount added is generally about 0.0 per IQ of the processing solution.
1-100. Good results can be obtained within this range. However, in general, when the amount added is too small, the bleaching promotion effect is small;
Also, if the amount added is too large than necessary, precipitation may occur and contaminate the color photosensitive material being processed.
Treatment liquid I (preferably 90.05 to 50 g per liter, more preferably 0.05 to 15 [r per treatment liquid IQ).

When the bleach accelerator of the present invention is added to a treatment bath having bleaching ability and/or a bath (pretreatment bath) that precedes a treatment bath having bleaching ability, it may be added and dissolved as is, but water, alkali, Generally, it is added after being dissolved in an organic acid, etc., and if necessary, even if it is added after being dissolved in an organic solvent such as methanol, ethanol, or 7-cetone, there is no effect on the bleach-fixing effect. do not have.

The bleaching accelerator of the present invention is represented by the general formula (13 to (Vl)), and among them, R2, Rco, R3, R8
, R9, A, B, D%z, z', R%R', and R and R', R, and R3, R4 and R1, and Q%
The heterocyclic residue formed by Q°, the ami7 group, the aryl group, the alkenyl group, and the alkylene group may each be substituted. Substituents include alkyl groups, aryl groups, alkenyl groups, cyclic alkyl groups, aralkyl groups, cyclic alkenyl groups, halogen atoms, nitro groups, cyano groups, flukoxy groups, aryloxy groups, carboxy groups, alkoxycarbonyl groups, and aryloxy groups. Carbonyl group, sulfo group, sulfomoyl group, carbamoyl group, acylamino group, heterocyclic residue, arylsulfonyl group, alkylsulfonyl group, alkylami 7 group, dialkylamino group, anilino group, N-furkylanilino group, N-7lylanyl group 7 groups, N-7 silanili 7 groups, hydroxy groups, and the like. Moreover, the above R1 to R5, R8, R1
, Z', R, and R' may also have a substituent, and examples of the substituent include all of those listed above except for the furkyl group.

As peroxides according to the present invention, hydrogen peroxide, percarbonates, perborates, and persulfates are preferably used.

Further, examples of these salts include potassium salts, natrirum salts, ammonium salts, and the like. The preferable amount of these used is 0.01 to 6.0 mol/! 1, more preferably 0.05 to 3.0 mol/Q.

The pH of the treatment solution containing peroxide used in the present invention is 0.1 to
51 in the 8.0 range! It is particularly preferably in the range of 0.5 to 5.5.

When the peroxide according to the present invention is decomposed, it easily becomes water and oxygen or sulfate, and can be easily and completely rendered harmless.

Furthermore, the materials used in the treatment solution according to the present invention are inexpensive and have excellent bleaching ability even when used at low concentrations.This advantage is directly reflected in terms of resources, with a low pollution burden. This makes it possible to easily supply an inexpensive bleaching solution or bleach-fixing solution.

The treatment liquid having bleaching ability of the present invention may contain organic acid ferric complex salt, ferric chloride, red blood salt, etc. for the purpose of further enhancing the bleaching ability. Available! Representative examples of organic acids that form 12-iron complex salts include the following.

(1) Ethylenediaminetetramethanephosphonic acid (2) Ethylenediaminetetramethynephosphonic acid (3) Noethylenedi7minepentaacetic acid (4) Noethylenetriaminepentamethylphosphonic acid (5
) Cyclohexanenoamine ethyl acetic acid (6) Cyclohexanediamine tetramethylene phosphonic acid (7) Triethylenetetramine hexaacetic acid (8) Triethylenetetramine hexamethylenephosphonic acid (9) Glycol ether diamine tetraacetic acid (io) Glycol ether diamine tetramethylene phosphonic acid acid (11) 1,2-diaminopropanetetraacetic acid (12) 1,
2-diaminopropane tetramethylenephosphonic acid (13N, 3-noaminopropan-2-ol tetraacetic acid (14) 1,3-diami/propan-2-ol tetramethylenephosphonic acid (15) ethylenediamine no-0-hydroxy 7-ethyl Dilylacetic acid (16) Ethylenediaminedi-0-hydroxyphenylmethylenephosphonic acid (17) 4minodiacetic acid (18) Iminonimethylenephosphonic acid (19) Methyliminoniacetic acid (20) Methyliminonimethylenephosphonic acid (21 ) Nitrilotriacetic acid (22) Nitrilotrimethylenephosphonic acid (23) Hydroxyethylethylenedi7minetetraacetic acid (24) Hydroxyethylethylenedi7minetetramethylenephosphonic acid (25) Nitrilotribrobionic acid (26) Hydroxyethylglycine ( 27) Hydroxyethyliminodiacetic acid (28) Hydroxyethylimino-nimethylenephosphonic acid (29) Ethylenediaminenoic acid (30) Ethylenediaminenibropionic acid Particularly preferred organic acids forming ferric salts of these organic acids The following can be mentioned.

(3) diethylenetriaminepentaacetic acid (5) cyclohexanenoaminetetraacetic acid (7) triethylenetetraminehexaacetic acid (1) ethylenediaminetetraacetic acid (11) 1,2-cyaminopropanetetraacetic acid (9) glycol etherdiaminetetraacetic acid These Organic acid ferric complex salts are free acids (hydrogen salts, sodium salts, potassium salts,
Alkali metal salts such as lithium salts, ammonium salts, or water-soluble amine salts such as triethanolamine salts are used, but potassium salts, sodium salts, and ammonium salts are preferably used. At least one type of these ferric complex salts may be used, but two or more types can also be used in combination. The amount used can be arbitrarily selected and needs to be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed, but it is generally lower than other 7-/polycarboxylate salts because of its high oxidizing power. Can be used in concentrations.

That is, it is preferably used in an amount of 0.01 mol or more, more preferably 0.05 to 0.6 mol, per IQ of the working liquid. Note that it is desirable to use the replenisher in a highly concentrated form with the highest solubility in order to achieve high concentration and low replenishment.

It is desirable that metal ions be supplied to the treatment liquid having bleaching ability of the present invention by any method in order to improve the bleaching ability. For example, it can be supplied in any form such as a halide, hydroxide, sulfate, phosphate, acetate, etc., but it is preferable to supply it as a complex salt of the chelating agent using the following compounds (hereinafter, these A metal compound that supplies metal ions is referred to as the metal compound of the present invention.) However, the supply method is not limited to these. As a chelating agent, organic polyphosphoric acid, 7-minoborboxylic acid, etc. It can be anything like.

[Exemplary compounds]

(A-1) Nickel chloride (A-2) Nickel nitrate (A-3) Nickel sulfate (A-4) Nickel acetate (A-5) Nickel bromide (A-6) Nickel iodide (A-7) Phosphorus Nickel acid (8 in A) Bismuth chloride (A-9) Bismuth nitrate (A-to) Bismuth sulfate (A-11) Bismuth acetate (A-12) Zinc chloride (A-13) Zinc bromide (A-14) Zinc sulfate (A-15) Zinc nitrate (A-16) Cobalt chloride (A-17> Cobalt nitrate (A-18) Cobalt sulfate (A-19) Cobalt acetate (A-20) Cerium sulfate (A-21) Chloride Magnesicum (A-22> Magnencum sulfate (A-23) Magnencum acetate (A-24) Calcium chloride (A-25) Calcium nitrate (A-26) Barium chloride (A-27) Barium acetate (A-28) Barium nitrate (A-29) Strontium chloride (A-30) Strontium acetate (A-31> Strontium nitrate (A-32) Manganese chloride (A-33) Manganese sulfate (A-34> Manganese acetate (A-35) Lead acetate ( A-36) Lead nitrate (A-37) Titanium chloride (A-38) Stannous chloride (A-39) Zirconium sulfate (A-40) Zirconium nitrate (A-41) Ammonium vanadate (A-42)
Ammonium metavananoate (A-43) Sodium tungstate (A-44) Ammonium tungstate (A-45) Aluminum chloride (A-46) Aluminum sulfate (A-47) Aluminum nitrate (A-48) Yttrium sulfate (A- 49) Yttrium nitrate (A-50) Yttrium chloride (A-51 > Samarium chloride (A-52) ??lium bromide (A-53) Samarium sulfate (A-54) Samarium acetate (A-55 > Ruthenium sulfate ( A-56) Ruthenium chloride These metal compounds of the present invention may be used alone, or two
More than one species can also be used together. The amount of metal ion used is preferably o,oooi moles to 2 moles, particularly preferably o,oooi moles to 1 mole, per IQ of the liquid used.

The processing liquid having bleaching ability of the present invention may contain various additives in addition to the peroxide of the present invention as a bleaching agent as described above. As additives for bleach-fixing properties, it is particularly desirable to contain alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, and the like. Also borate,
pH buffering agents such as oxalate, acetate, carbonate, phosphate, solubilizing agents such as triethanolamine, acetylacetone, phospho-7 carboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, alkyl amine It is possible to appropriately add substances known to be added to ordinary bleaching solutions, such as polyethylene oxides and polyethylene oxides.

The processing liquid having bleaching ability of the present invention includes a bleach-fixing liquid having a composition in which a small amount of a halide such as potassium bromide is added, or conversely, a composition having a composition in which a large amount of a halide such as potassium bromide or ammonium bromide is added. It is also possible to use a special bleach-fix solution having a composition consisting of a combination of the bleaching agent of the present invention and a large amount of a halide such as potassium bromide.

Silver halide fixing agents to be included in the bleach-fixing solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and thiosulfate, which are used in ordinary fixing processes. Typical examples include 100sulfates such as ammonium osulfate, 1000sulfates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, 1000sulfur, thioethers, and high concentrations of bromide and iodide. . These fixatives are 5g
/11 or more, preferably 50g/! It can be used in an amount within a range of 1 or more, more preferably 70 g/Q or more.

In addition, the bleach-fix solution contains various l)H such as boric acid, borax, 17um hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. A buffering agent may be contained alone or in combination of two or more types, and various optical brighteners, antifoaming agents, or antifoaming agents may also be contained. It also contains preservatives such as hydroxylamine, hydranone, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, other additives, and organic solvents such as methanol, dimethylformamide, and trimethylsulfoxide. You can force it.

Other desirable compounds that can be added to the bleaching solution of the present invention to promote bleaching properties include tetramethylurea, trismethylamide phosphate, ε-caprolactam, N-methylpyrrolidone, N-methylmorpholine, and tetraethylene. glycol mono-7 enyl ether, acetonitrile,
Examples include glycol monomethyl ether and the like.

In the processing method of the present invention, it is preferable to carry out the bleaching of the present invention immediately after color development; however, after color development,
The method of the present invention includes independent steps such as washing, rinsing, or stopping, but
Development here means black-and-white development and color development, and cases involving only color development or those including both black-and-white development and color development are also used.

The above steps do not necessarily have to be consecutive, and various processing steps can be included before and after each of the above steps. Such a process is called an auxiliary process, and the auxiliary process includes a stop bath,
There are stop and fix baths, hard + i baths, neutralization towers, water washing, rinsing, image stabilization baths, etc.

Bleaching according to the invention 8! Alternatively, from the viewpoint of simplifying the processing steps, it is desirable to apply the bleach-fix solution to a processing process in which both color development and development are followed by bleaching or bleach-fixing. However, in some cases, it is more preferable that the bleach-fix solution of the present invention does not contain a developing agent or halogen ions, and depending on the type of color photosensitive material to be processed and other requirements, water washing treatment, rinsing treatment, etc. may be performed after color development.
It is easier to carry out bleach-fixing after appropriately passing through one or more treatments such as a stop treatment, a bleach-fixing treatment, a pre-bleach-fixing bath (a so-called Fundigi 3ner for efficient bleach-fixing), or a hardening treatment. desirable.

Further, for a special purpose, after the bleach-fixing process, it is optional to perform a separate process with a bleach-fixing solution or a fixing solution that is not according to the present invention. That is, it is optional to place a bleach or bleach-fix solution according to the present invention at an irritating process location to remove image silver.

Next, a specific processing example will be shown, but the present invention is not limited to the following process example.

■Dural mater - Neutralization - One stop of development - One stop of washing - One stop of color development -
Washing - Final processing - Drying - Development - Washing - Reversal -
Color development-11! - [i Constant wear, washing with water, final treatment, drying ■ Color development - Continuous washing, washing with water, final treatment, drying ■ Color development - ... - Washing with a small amount of water, constant wear, washing with water, washing with water, final treatment, drying ■ Color development - Section 1 - Water washing - Final treatment - Drying - Color development - Final treatment - Drying - Color development - Continuous drying - Final treatment - Drying What is final treatment? The waterless washing process described in Nos. 57-8543, 58-57903, etc. is carried out, and the waterless washing process is particularly advantageous in terms of resource saving and image preservation.

The photographic constituent layers of the color light-sensitive material of the present invention (gelatin film thickness) refer to the photographic constituent layers excluding the support, i.e., the subbing layer, the halecitane prevention layer, the intermediate layer, at least three emulsion layers, one filter layer, and the protective layer. This is the total thickness of all the wood-philic colloid layers, and the thickness of the dried photographic constituent layer. The thickness is measured with a micrometer, and in the present invention the total thickness of the photographic constituent layers is 25 μm or less, preferably 22 μm or less, particularly preferably 20 μm or less, and most preferably 18 μm or less.

The silver halide of the silver halide emulsion layer used in the present invention contains at least 0.5 mol% of silver iodide grains, but it maximizes the sensitivity and photographic properties of the color light-sensitive material and the bleach-fixing performance of the present invention. In order to obtain the desired photographic properties and bleach-fixing properties, silver iodide is preferably used in an amount of 3 mol % to 25 mol % from α. In the present invention, if the content exceeds 25 mol%, the photographic properties are more favorable, but the bleach-fixing properties are markedly lowered. In the present invention, it is more preferable that silver iodide be contained in an amount of 3 mol % to 20 mol %.

The antihalation black colloidal silver dispersion layer used in the present invention has a sufficiently high optical density in the visible region (especially red light) for light incident from the support surface or emulsion surface of the color photosensitive material. It is necessary to have it.

Further, it is necessary that the color light-sensitive material has a sufficiently low reflectance to light incident on the emulsion surface.

From the viewpoint of reflectance and bleach-fixing properties, it is desirable that the colloidal silver particles be sufficiently fine, but since the absorption becomes yellow to yellowish brown and the optical density against red light does not increase, it is necessary to use coarse particles to some extent. Therefore, it is thought that ethical development using these silver particles as nuclei is likely to occur, and that the bleach-fixing properties at the boundary with the silver halide emulsion layer deteriorate. If the silver halide emulsion layer contains at least 3 mol % of silver iodide grains in vt, bleaching is performed if the silver halide emulsion layer closest to the support contains at least 3 mol % of silver iodide grains. It can be seen that the method of the present invention is effective because the phenomenon of deterioration of fixing properties becomes noticeable and becomes noticeable in multilayer color light-sensitive materials having three or more silver iodide-containing emulsion layers.

The photosensitive silver helodenide emulsion used in the present invention may be doped with various metal salts or metal complex salts during the formation of silver halide precipitate, during grain growth, or after the completion of grain growth. For example, metal salts or complex salts such as gold, platinum, palladium, irizoum, rhodium, bismuth, cadmium, copper, and combinations thereof can be used.

Excess halogen compounds generated during the preparation of the emulsion or by-products or unnecessary salts and compounds such as nitrates and ammonium may be removed.

As a method for removal, a nude washing method, a dialysis method, a coagulation precipitation method, etc., which are commonly used in general emulsions, can be used as appropriate.

Further, the emulsion used in the present invention can be subjected to various chemical sensitization methods that are applied to general emulsions.

Namely, activated gelatin; noble metal sensitizers such as water-soluble gold salts, water-soluble platinum salts, water-soluble palladium salts, water-soluble rhodium salts, water-soluble iridium salts; sulfur sensitizers; selenium sensitizers; polyamines, 1s chloride Chemical sensitization can be carried out using chemical sensitizers such as reduction sensitizers such as, alone or in combination. Further, this silver halide can be optically sensitized to a desired wavelength range. There are no particular limitations on the method for optically sensitizing the emulsion of the present invention (for example, cyanine dyes such as zeromethine dyes, monomethine dyes, trimethine dyes, etc.). Optical sensitization can be achieved by using optical sensitizers such as dyes or merocyanine dyes alone or in combination (for example, supersensitization).These techniques are described in U.S. Pat. 9
No. 12.329, No. 39397,060, No. 3゜61
No. 5.635, No. 3,628,964, British Patent No. 1,
No. 195,302, No. 1,242,588, No. 1, 2
No. 93,862, West German Patent (OLS) 2.030,32
No. 6, No. 2,121,780, Special Publication No. 43-4936
No. 44-14030, etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material.

The average grain size of the silver halide grains used in the present invention is preferably 0.5 μm to 3 μm, and can be grown using a solvent such as ammonia, thioether, thiourea, etc., if necessary. .

In addition, the emulsion used in the present invention is disclosed in JP-A-53-10372.
No. 5, No. 59-133540, No. 59-162540
It is also preferable to contain epitaxially bonded silver halide grains as described in No.

The silver halide emulsion can contain various commonly used additives depending on the purpose. For example, azaindenes,
triazoles, tetrazoles, imidazoliums,
Stabilizers and anti-capri agents such as tetrazolium salts and polyhydroxy compounds; hardening agents such as aldehyde-based, aziridine-based, inoxazole-based, vinylsulfone-based, acryloyl-based, carbodiimide-based, maleimide-based, methanesulfonic acid ester-based, triazine-based, etc. Agent; benzyl alcohol,
Development accelerators such as polyoxyethylene compounds; image stabilizers such as chroman, claman, bis7er/-el, and phosphite esters; waxes, glycerides of higher fatty acids, higher alcohol esters of higher fatty acids, etc. There are lubricants, etc. In addition, anionic, cationic, nonionic, or A variety of both sexes can be used. In particular, it is preferable that these surfactants are eluted into a processing solution having bleaching ability. Effective antistatic agents include rare acetyl cellulose, styrene perfluoro r:l flukyrundium maleate copolymer, and alkali salts of reaction products of styrene-maleic anhydride copolymer and p-7 minobenzenesulfonic acid. It is. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. It is also possible to use colloidal silicon oxide.

Examples of latexes added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc. and monomers having ethylene groups.

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

In the color light-sensitive material of the present invention, hydrophilic colloids used to prepare emulsions and other hydrophilic colloid layer coating solutions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, albumin, casein, etc. proteins, cellulose derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose, starch derivatives,
Any single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl alcohol, and polyacrylamide are included.

Examples of the support for the color photosensitive material of the present invention include a glass plate, a polyester film such as cellulose acetate, cellulose nitrate or polyethylene tere-7-thalerate, a polyamide film, a polycarbonate film, a polystyrene film, etc. (For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or combined with a reflective material), and these supports are appropriately selected depending on the intended use of the photosensitive material. .

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the silver halide emulsion layer and other photographic constituent layers used in the present invention.

Also, U.S. Patent Nos. 2,761,791 and 2,941,8
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 98.

The silver halide emulsion of the present invention is a combination of cyan, magenta, and yellow couplers with the silver halide emulsion of the present invention, which has been color-sensitized and adjusted to have red sensitivity, green sensitivity, and blue sensitivity, in order to be applied to color light-sensitive materials. It is sufficient to apply a method and a material used for color photosensitive materials, such as incorporating the same.

Color photosensitive materials to which the bleach-fix solution of the present invention can be applied include internal development methods (see U.S. Pat. No. 2,376.679 and U.S. Pat. No. 2,801.171) in which a color former is contained in the photosensitive material, as well as , an external development method in which a coloring agent is contained in the developer (U.S. Pat. No. 2,252,718, U.S. Pat. No. 2,592.2)
No. 43 and No. 2,590,970).

Further, as the coloring agent, any coloring agent generally known in the art can be used. For example, cyan coloring agents are those based on a naphthol or phenol structure and form indoaniline dyes through coupling, magenta coloring agents are those having a skeletal structure of a 5-pyrazolone ring with an active methylene group, and yellow coloring agents are As examples, those having an acylacedoanilide structure such as benzoylacedoanilide and pivalyl7ceto7nilide having an active methylene chain and having a substituent at the coupling position,
You can use any one you don't have. Thus, as the color former, both so-called 2-equivalent couplers and 4-equivalent couplers can be used.

The black-and-white developer that can be used in the processing of the present invention is a commonly known black-and-white first developer used in processing color photographic materials, or a developer used in processing black-and-white photographic materials. It can contain various additives that are generally added to black and white developers.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol, and hydroquinone, preservatives such as sulfites, and accelerators such as alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. , inorganic or organic inhibitors such as potassium bromide, 2-methylbenlimigsol, methylbenzthiazole, water softeners such as polyphosphates, and surface overdevelopment consisting of trace amounts of iodides and mercapto compounds. Inhibitors and the like can be mentioned.

The aromatic primary amine color developing agent used in the color developing solution used before processing with the bleach-fix solution of the present invention is:
Includes a variety of those widely used in various color photographic processes. These developers include amino 7-el/- and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, because they are more stable than the free state. In addition, these compounds are generally preferably used at a concentration of about 0.1 g to about 30 g for color developer IQ, more preferably about 1 g to about 15 g for IQ. Use at a concentration of

Examples of the 7 mm / 7 x /-le type developer include 0-7 mino 7-el, p-7 minophenol, 5-7 mino-7-2-hydroxytoluene, and 2-7 mino-3-hydroxytoluene. , 2-hydroxy-3-7mi/-1,4-
Contains trimethylbenzene, etc.

A particularly useful aromatic primary amine color developer is N.

It is an N-dialkyl-p-phenylenenoamine compound, and the furkyl group and phenyl group may be substituted or unsubstituted.

Among them, a particularly useful compound is N,N-noethyl-p-phenylenenoamine! Acid m, N-/thi-p-phenylenediamine hydrochloride, NIN-7 methyl-p-phenylenediamine hydrochloride, 2-amino/-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl- N-
β-methanesulfonamidoethyl-3-methyl-4-ami/aniline sulfate, N-ethyl-N-β-hydroxyethyl 7-aniline sulfate, 4-7minor 3-methyl-N,N-diethylaniline Sulfate, 4-amino-N-
(Methoxyethyl)-N-ethyl-3-methylaniline-p-)luenesulfonate and the like can be mentioned.

The paraphenylenediamine color developing agent is preferably mixed into the bleach-fix solution of the present invention.

The alkaline color developing solution used before the treatment with the processing solution having bleaching ability of the present invention includes, in addition to the above-mentioned aromatic primary amine color developing agent, various kinds of color developing solutions that are usually added to the color developing solution. Ingredients such as alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benol alcohol, ethylenetriaminepentaacetic acid, A water softener and a thickening agent such as 1-hydroxyethylidene-1,1-diphosphonic acid may optionally be contained. The pH of this color developing solution is usually 7 or higher, most commonly about 10 to 7.
It is about 13.

The processing solution having bleaching ability according to the present invention includes color paper, color negative film, color positive film, color reversal film for slides, color reversal film for movies,
It can be applied to color photosensitive materials using the emulsion of the present invention, such as color reversal films for TVs and color reversal papers, but it is particularly suitable for processing high-sensitivity color photosensitive materials with a total coated silver amount of 2016 g/d112 or more. Are suitable.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to examples, which will explain how the present invention can be carried out! ! ! Example 1 Although the method is limited, black colloidal silver halation is applied from the support side with various auxiliary layers interposed, following the layer structure adopted in the industry for high-sensitivity silver halide color photographic light-sensitive materials. A prevention layer, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer, and a monodisperse high-sensitivity halogen layer is formed on the outermost side of the blue-sensitive silver halide emulsion layer. A silver emulsion layer was provided. That is, although a sample was prepared according to the following, the film thickness Ill! Samples with varying dry film thicknesses were prepared.

However, the following are standard coating conditions, and each formulation was changed to allow for changes in film thickness.

Layer 1: A dispersion of 0.8 g of black colloidal silver, which is highly absorbent to light in the wavelength range of 400 to 700 nm, is prepared by reducing silver nitrate with hydroquinone as a reducing agent in 3 g of gelatin, and an antihalation layer is applied. did.

(Dry film thickness 2.0 μm) Layer 2: Intermediate layer made of gelatin. (Dry film thickness 0.8
μ So) Layer 3: 1.5 g of low-sensitivity red-sensitive silver iodobromide emulsion (^gI; 8 mol%), 1.6 g of gelatin and 0
．． 80 g of 1-hydroxy-4-(β-methoxyethylami7carponylmethoxy)-N-[δ-(2,4-the-t-amyl72/xy)butyl 1-2-su7mide (hereinafter , cyan coupler (c-i)), 0.02
8 g of 1-hydroxy-4-[4-(1-hydroxy-
8-7 Cetamido 3,6-disulfo-2-su7tylazo)phenoxy]-N-[δ-(2,4-di-amyl7
E/xy)butyl]-2-su7tamide disodium (hereinafter referred to as colored cyan coupler (CC-1))
A low-sensitivity red-sensitive silver halide emulsion layer containing 0.4 g of tricresyl phosphate (hereinafter referred to as TCP) dissolved in it.

Layer 4: Bow, 1g of high-sensitivity red-sensitive silver iodobromide emulsion (heg
I; 7 mol%), 1.2 g of gelatin and 0.23 g
of cyan coupler (C-1), 0.15 g of T in which 0.020 g of colored cyan coupler (CC-1) was dissolved.
A highly sensitive red-sensitive silver helodenide emulsion layer containing CP.

Layer 5-0-0.04 g of dibutyl 7-talate (hereinafter referred to as D
BP) and 1.2 g of gelatin.

Layer 6: 1.6 g of low-sensitivity green-sensitive silver iodobromide emulsion (HgI; 15 mol %), 1.7 g of gelatin and 0.3
0 g of 1-(2,4,6-dolichlorophenyl)-3-
[3-(2,4-di-t-7milphenoxy7cetamido)benzenamide]-5-pyrazolone (hereinafter referred to as magenta coupler (M-1)), 0.20 g of 4°4
-methylenebis-11-(2,4,6-)lichlorophenyl)-3-(3-(2,4-not-amylphenoxyacetamide)benzenamide]-5-pyrazolone(
Hereinafter referred to as magenta coupler (M-2)), 0.06
6 g of 1-(2,4,6-dolichlorophenyl)-4-
(1-su7tylazo)-3-(2-chloro-5-octadecenylsuccinimideanili/)-5-pyrazolone (
(hereinafter referred to as colored magenta coupler (CM-1))
A low-sensitivity green-sensitive silver halide emulsion layer containing 0.3 g of TCP in which three types of couplers are dissolved.

Layer 7: 5g of high-sensitivity green-sensitive silver iodobromide emulsion (heg
1; 11 mol%), 1.9 g of gelatin and 0.09
High sensitivity containing 0, 12H TCP dissolved in 3g of magenta coupler (M-1), 0.0948g of magenta coupler (M-2), and 0.049g of colored magenta coupler (CM-1). Green-sensitive silver halide emulsion layer.

Scrap 8: One layer of Yea-filter containing 0.2 g of yellow colloidal silver, 0.11 H DBP in which 0.2 g of antifouling agent (HQ-1) was dissolved and 2.1 g of gelatin.

(Dried 11141.28 rings) Layer 9...0.95 g of low-speed blue-sensitive silver iodobromide emulsion (
hegI; 6 mol%), 1.9 g of gelatin and 1.8
4 g of α-[4-(1-bentrue-2-phenyl-3,
5-Thuoxo 1,2.4-)riazolidinyl) 1-a
-Bivaloyl-2-chloro-5-[γ-(2,4-not-t-amylphenoxy)butanamide 1 acetanilide (hereinafter referred to as yellow coupler (Y-1)) was dissolved in 0,93. A low-speed blue-sensitive silver halide emulsion layer containing DBP.

Layer 10... Bow, 2g high sensitivity weight l! A high-sensitivity blue-sensitive silver iodobromide emulsion containing 0.23 g of DBP in which a blue-sensitive silver iodobromide emulsion (8 g; 7 mol %), 2.0 g of gelatin, and 0.46 g of yellow coupler (Y-1) were dissolved. Silver halide hole cuttings.

Layer 11: Second protective layer made of gelatin.

Scrap 12...1st hoard w1 containing 2.3 g of gelatin
layer.

The dry film thicknesses of the photographic constituent layers of the finished samples were 35 μm, 30 μm, 127 g, and 25 μ, 1122 g, respectively.
There were eight types: 0μm, 18μm, and 15μm. This was designated as Sample No. 1 to 8. However, the film thickness and black colloidal silver content of the antihalation layer and the film thicknesses of the gelatin intermediate layer and the yellow filter layer were not changed at all.

Another sample was prepared by coating the same emulsion on a transparent polyethylene terephthalate film base without the bottom colloidal silver antihalation layer. The samples are numbered in descending order of M thickness.

It was set as 9 to 16. The average amount of coated silver for all samples is 50-58m
g/da”.

Each sample was treated using a treatment solution prepared according to the following treatment steps and the following formulation.

Processing process Temperature Time color development 41℃ 3 minutes pre-bleach bath 38℃ 30 seconds bleach bath
Wash with water at 38℃ for 10 seconds to 5 minutes 33
℃ 1 minute fixation 33
℃ 3 minutes Wash with water 33
℃ Stable for 2 minutes 33℃
30 seconds [Color developer] Potassium carbonate 3og Sodium sulfite 2.0g Hydroxylamine sulfate 2,0g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0g Potassium bromide 1.2g Magnesium chloride 0.6g Sodium hydroxide
3.4 g N-ethyl-N-β-hydroxyethyl-3-methyl-4-7 minoaniline sulfate 4.6 g water was added to make IQ, and the pH was adjusted to 10.1 with sodium hydroxide.

[Pre-bleaching bath]

Sodium sulfite 10. og sodium acetate 8.0g glacial acetic acid
Add 23mQ water and make 1(l)
The pH was adjusted to 3.8 with sodium hydroxide or acetic acid.

[12 Shiranami] Sodium persulfate eog sodium chloride 20g Sodium dihydrogen phosphate (anhydrous) 9.0g phosphoric acid (85%)
2.5mQ1-hydroxyethylidene-I+1-diphosphonic acid (60%) 1.0g
Gelatin 0.5° Add water to make 1Q, and dilute with 1 part of sodium hydroxide or phosphoric acid.
H2,31 d adjustment.

[Fixer]

Sodium periosulfate 150g Sodium sulfite 12g Add water
ll.

[Stabilizing liquid]

Formalin (37% solution) 10- Add water to obtain IQ.

1.5 g of the exemplified compound of the present invention per IQ as shown in Table 1 was added to the pre-bleaching bath, and the bleaching time was changed in two steps of 1 minute and 3 minutes, and the bleaching ability was determined from the amount of residual i. The six compared results are shown in Table 1.

Table 1 As is clear from the results in Table 1, in the case of a multilayer silver halide color photographic light-sensitive material having an antihalation layer of black colloidal silver, if the film thickness of the photographic constituent layer (gelatin film thickness) is large, bleaching is not possible. It can be seen that although the properties are obviously poor, they rapidly improve as the thickness of the photographic constituent layer (gelatin film) becomes thinner, and the change is greatest around 25 μm. In addition, the effect of the bleaching accelerator is not effective when the thickness of the photographic constituent layer (gelatin film thickness) is large, but it is clearly effective in the case of a thin photographic constituent layer (gelatin film Fq-). It turns out that it will be done.

On the other hand, in a silver halide color photographic light-sensitive material that does not have a black colloidal silver antihalation layer, the thickness of the photographic constituent layer (
It can be seen that there is almost no effect on gelatin film thickness (gelatin film thickness) and that the time required to complete bleach-fixing is extremely short. It is difficult to put this into practical use as a high-sensitivity photographic material.

Example g#2 The same samples as sample Nos. 1 to 8 of Example 1 were prepared. However, the silver iodide mol% of the red-sensitive silver iodobromide emulsions No. 3M and No. 4711 (each was 8.7 mol%) was 1 mol%? It was changed to 3 mol%, 5 mol%, 10 mol%, and 20 mol%.

The rest was the same as in Example 1, with samples Nos. 17 to 56. The same treatment as in Example 1 was performed, and the results are shown in Table 2. However, the bleaching accelerator added to the pre-bleaching bath was the exemplified compound 1l-1tE of the present invention.

Below is Table 2. As is clear from Table 2, when the silver iodide mol% of the red-sensitive emulsion adjacent to the ration colloidal silver layer is low, the film thickness of the photographic constituent layer (gelatin film thickness) is low. ), but as the silver iodide mole % increases and the film thickness increases, the amount of silver bleached by persulfate decreases significantly, and desilvering defects become more severe.

On the other hand, it can be seen that when the film thickness is 25 μm or less, favorable bleaching properties are maintained without being affected by the increase in silver iodide mole %.

Example 3 Samples Nos. 011 to 8 of Example 1 were used, and a pre-bleach bath containing 1.5 g/Q of the exemplary compound of the present invention as shown in Table 3 and 1.5 g/Q of thiourea, a known bleach accelerator, was used. [Processed using a pre-bleach bath with 1/Q addition. As a result (Table 3), the compounds of the present invention showed more preferable bleaching properties at film thicknesses within the range of the present invention in all cases than the compounds other than the compounds of the present invention.

Table 3

Claims (1)

[Scope of Claims] (1) A photographic constituent layer including an antihalation layer containing black colloidal silver and a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer is provided on a support, and the halogen A silver halide color photographic light-sensitive material in which the layer closest to the antihalation layer among the silver emulsion layers contains silver halide grains containing silver iodide and the total thickness of the photographic constituent layers is 25 μm or less is imaged. 1. A method for processing a silver halide color photographic light-sensitive material, which comprises performing a development treatment after exposure to light, and processing with a processing solution having a silver bleaching ability and containing peroxide as a bleaching agent. (2) Claim 1, characterized in that the treatment bath having bleaching ability and/or the bath preceding the bath contains at least one compound represented by the following general formulas [I] to [VI]. A method for processing a silver halide color photographic light-sensitive material as described in . 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. ▼ General formula [
VI]▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the above general formula, Q is a heterocycle containing one or more N atoms (
Represents the atomic group necessary to form a 5- to 6-membered unsaturated ring (including those with at least one fused ring), and A is ▲Mathematical formula, chemical formula, table, etc.▼, ▲Mathematical formula, chemical formula ,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲Mathematical formulas, chemical formulas, tables, etc. ),
B represents an alkylene group having 1 to 6 carbon atoms, M represents a divalent metal atom, and X and X' are =S, =O or =NR''
R'' represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (
(including those with at least one 5- to 6-membered unsaturated ring condensed thereto) or an amino group, Y represents >N- or >CH-, Z represents a hydrogen atom, an alkali metal atom,
Ammonium group, amino group, nitrogen-containing heterocyclic residue or ▲
There are mathematical formulas, chemical formulas, tables, etc. Represents ▼, Z' represents Z or an alkyl group, R_1 is a hydrogen atom, and has 1 carbon number
~6 alkyl groups, cycloalkyl groups, aryl groups,
Represents a heterocyclic residue (including those to which at least one 5- to 6-membered unsaturated ring is fused) or an amino group,
R_2, R_3, R_4, R_5, R and R' are each
Hydrogen atom, alkyl group having 1 to 6 carbon atoms, hydroxy group,
represents a carboxyl group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, or an alkenyl group, provided that R_4 and R_5 may represent -B-SZ, or R and R', R
_2 and R_3, R_4 and R_5 may each be cyclized with each other to form a heterocyclic residue (including one in which at least one 5- to 6-membered unsaturated ring is fused thereto). R_6 and R_7 each have ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where R_9 is an alkyl group or -(CH_2)n_8
Represents SO_3^■ (However, R_8 is -(CH_2)n_
When 8SO_3^■, l represents 0 or 1. )G＾■
are anions, m_1 to m_4 and n_1 to n_
8 represents an integer from 1 to 6, and m_5 represents an integer from 0 to 6. R_8 represents a hydrogen atom, an alkali metal atom, ▲numerical formula, chemical formula, table, etc.▼ or an alkyl group. However, Q' has the same meaning as Q above. D represents a simple bond, an alkylene group or vinylene group having 1 to 8 single primes, q represents an integer of 1 to 10, multiple D's may be the same or different, and the ring formed with the sulfur atom is , and may be further fused with a 5- to 6-membered unsaturated ring.The compounds represented by the above general formula include enolized compounds and salts thereof. [3] The method for processing a silver halide color photographic light-sensitive material according to claim 2, wherein the compounds represented by the general formulas [I] to [VI] are the following compounds. (a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (c) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (d) ▲ Numerical formulas, chemical formulas, tables, etc. Yes▼(e)HS-
CH_2CH_2-COOH (f) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (g) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (h) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (i) ▲ Mathematical formulas, chemical formulas, There are tables, etc. ▼ (j) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (k) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (l) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (m) ▲ Mathematical formulas, There are chemical formulas, tables, etc.▼ (n)▲There are mathematical formulas, chemical formulas, tables, etc.▼ (o)▲There are mathematical formulas, chemical formulas, tables, etc.▼ (p)▲There are mathematical formulas, chemical formulas, tables, etc.▼ (q)▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (r)▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (s)▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (t)▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (u ) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ or (v) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (4) The silver halide color photographic light-sensitive material is characterized in that the thickness of the photographic constituent layer is 22 μm or less. A method for processing a silver halide color photographic material according to claim 1, 2 or 3. (5) The method for processing a silver halide color photographic material according to claim 4, wherein the thickness of the photographic constituent layer of the silver halide color photographic material is 20 μm or less. (6) The method for processing a silver halide color photographic material according to claim 5, wherein the thickness of the photographic constituent layer of the silver halide color photographic material is 18 μm or less. (7) Each of the silver halide emulsion layers contains 3 mol % to 25 mol %
7. A method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 6, characterized in that it contains silver halide grains containing mol % of silver iodide. (8) The silver halide color photographic light-sensitive material according to any one of claims 1 to 7, wherein the bleach-fixing treatment is carried out after color development and after the fixing treatment. processing method.